Esplora E-book

Categorie

Esplora Audiolibri

Categorie

Esplora Riviste

Categorie

Esplora Documenti

Categorie

0 valutazioniIl 0% ha trovato utile questo documento (0 voti)

71 visualizzazioni203 pagineDr. Andrea Caligiana's PhD thesis in Chemical Sciences.
University of Perugia (Italy), year 2003.

© © All Rights Reserved

PDF, TXT o leggi online da Scribd

Dr. Andrea Caligiana's PhD thesis in Chemical Sciences.
University of Perugia (Italy), year 2003.

© All Rights Reserved

0 valutazioniIl 0% ha trovato utile questo documento (0 voti)

71 visualizzazioni203 pagineDr. Andrea Caligiana's PhD thesis in Chemical Sciences.
University of Perugia (Italy), year 2003.

© All Rights Reserved

Sei sulla pagina 1di 203

UNIVERSITA

Dottorato di Ricerca in Scienze Chimiche

Sturmian Orbitals in

Quantum Chemistry

Andrea Caligiana

Coordinatore:

Relatore:

Ottobre 2003

Ringraziamenti

Desidero ringraziare sentitamente numerose persone,

che hanno contribuito allo svolgimento del mio dottorato

ed alla realizzazione di questa tesi: innanzitutto il Prof.

Aquilanti, la cui disponibilita a venirmi incontro e sostenermi nei momenti dicili e stata ancora piu importante

di qualunque competenza scientica un relatore possa

trasmettere. Lo stesso dicasi per Simona (Prof.ssa Cavalli), che non ha mai smesso di infondermi ducia e

di aiutarmi a conoscere me stesso. Una parte considerevole dei risultati presentati e dovuta alla preziosa

collaborazione con il Prof. John Avery dell'Universita

di Copenhagen. Il prof. Tarantelli mi ha tante volte

trasmesso parte delle sue conoscenze non solo al Dipartimento di Chimica, ma anche durante lunghi viaggi a

bordo del bus n.9. L'estate del 2002, trascorsa al Dipartimento di Chimica di Cambridge(UK), e stata un periodo stimolante e piacevole, oltre che scienticamente

produttivo: ringrazio il Prof. Handy che mi ha permesso

di lavorare nel suo gruppo di ricerca e di alloggiare al

St. Catharine's College, ed i suoi collaboratori Rudolph

Burcl e David Tew.

Dopo i `senior', passo a menzionare coloro con cui

(oltre al luogo di lavoro) ho condiviso svariate serate

divertenti,... Andrea Beddoni, Andrea Lombardi, An-

Benedetti, Massimiliano Bartolomei, Loriano Storchi,

Noelia, Valentina Piermarini...

Voglio inne ringraziare i miei familiari: e soprattutto

a loro che devo il raggiungimento di questo traguardo,

ed e a loro che dedico questa tesi.

Contents

Introduction

5

1 Hydrogenic Elliptic Orbitals, Coulomb

9

1.1 Introduction . . . . . . . . . . . . . . . . . . . . . .

1.2 Polar and Parabolic Sturmians . . . . . . . . . . . .

1.3 The conservation of parity in the trasformation between polar and parabolic orbitals . . . . . . . . . .

1.4 Spheroidal Sturmians . . . . . . . . . . . . . . . . .

1.5 Spheroelliptic Sturmians . . . . . . . . . . . . . . .

1.6 Conclusion . . . . . . . . . . . . . . . . . . . . . . .

Bibliography . . . . . . . . . . . . . . . . . . . . . . . .

10

16

24

31

39

48

53

2.1 Introduction . . . . . . . . . . . . . . . . . . . . . .

2.2 Background . . . . . . . . . . . . . . . . . . . . . .

2.3 The Canonical Bases of O(4) . . . . . . . . . . . . .

2.3.1 Asymmetric Parametrizations : Spherical and

Zeeman Sets . . . . . . . . . . . . . . . . . .

2.3.2 Symmetric Parametrizations . . . . . . . . .

2.3.3 The Scheme of the Orthogonal Transformations among the Canonical Bases of O(4) . .

2.4 Conservation of parity in the transformations among

momentum space Sturmians . . . . . . . . . . . . .

2.4.1 Spherical and Stark Basis Sets . . . . . . . .

1

60

62

67

69

75

76

80

81

2

2.4.2 Zeeman Basis Sets . . . . . . . . . . . . . .

2.5 The elliptic bases of O(4) . . . . . . . . . . . . . . .

2.5.1 Spheroelliptic Coordinates and Basis sets . .

2.5.2 Elliptic Cylindrical Coordinates of Type I and

II . . . . . . . . . . . . . . . . . . . . . . . .

2.6 Summary and concluding remarks . . . . . . . . . .

Bibliography . . . . . . . . . . . . . . . . . . . . . . . .

82

87

88

90

95

99

3.1

3.2

3.3

3.4

Introduction . . . . . . . . . . . . . . . . . . . . . .

Free atoms . . . . . . . . . . . . . . . . . . . . . . .

Atoms in external elds . . . . . . . . . . . . . . .

Electronic integrals between Sturmian congurations

3.4.1 Overlap Integrals . . . . . . . . . . . . . . .

3.4.2 Matrix elements of one-electron operators .

3.4.3 Matrix elements of two-electron operators .

3.5 On the choice of the `energy' in the denition of the

basis set . . . . . . . . . . . . . . . . . . . . . . . .

3.6 Examples . . . . . . . . . . . . . . . . . . . . . . .

Bibliography . . . . . . . . . . . . . . . . . . . . . . . .

106

107

111

112

113

114

116

120

122

124

iteration schemes

127

4.2 Two-center Nuclear Attraction Integrals S and W . 129

4.3 Solution of one-electron multicenter wave equation;

comparison among performances of dierent iterations134

4.4 Further remarks and conclusions . . . . . . . . . . . 140

Bibliography . . . . . . . . . . . . . . . . . . . . . . . . 142

an Introduction

147

5.1 Introduction . . . . . . . . . . . . . . . . . . . . . .

5.2 Sturmian basis sets for atomic and molecular calculations . . . . . . . . . . . . . . . . . . . . . . . . .

5.2.1 Many-center many-electron systems . . . . .

5.2.2 The integrals. Relationships with Slater-type

orbitals . . . . . . . . . . . . . . . . . . . .

5.3 Further remarks and conclusions . . . . . . . . . . .

148

151

151

156

163

3

Appendix . . . . . . . . . . . . . . . . . . . . . . . . . . 164

Bibliography . . . . . . . . . . . . . . . . . . . . . . . . 166

pseudorotation motion in PF5

169

6.1 Introduction . . . . . . . . . . . . . . . . . . . . . .

6.2 Geometry optimization and harmonic frequencies .

6.3 Tunnelling splittings in PF5 . . . . . . . . . . . . .

6.4 Anharmonic vibrations of PF5 . . . . . . . . . . . .

6.5 MULTIMODE with the Reaction Path Hamiltonian

6.6 Conclusion . . . . . . . . . . . . . . . . . . . . . . .

Bibliography . . . . . . . . . . . . . . . . . . . . . . . .

Conclusions

170

171

174

181

187

190

192

197

Bibliography . . . . . . . . . . . . . . . . . . . . . . . . 200

Introduction

The fundamental scope of quantum chemistry is the determination of the wavefunctions for the stationary states of electrons

in the presence of xed nuclei, eventually including the eect of

external elds and perturbations. Then, according to the BornOppenheimer approximation, the electronic wavefunctions may be

used for the construction of potential energy surfaces, on which

the motion of the nuclei can be studied, by quantum or classical

techniques.

The electronic wavefunctions are obtained solving a time independent Schrodinger equation by methods that include the use

of sets of monoelectronic functions (orbitals) as basis sets for the

approximation of the solutions. The kind of functions used as electronic orbitals aects strongly the convergence rate and accuracy

of numerical procedures.

The only chemical system whose Schrodinger equation is analytically solvable is the hydrogen atom. In the early days of quantum

chemistry, scientists tried to use hydrogenic functions (i.e. the solutions of the Schrodinger equation for the hydrogen atom) and

5

6

similar functions as orbitals to approximate more complex wavefunctions, incurring in the inconvenient of complicated two-electron

integrals. In the last decades, instead, linear combinations of Gaussian functions have been used as electronic orbitals, replacing all

the other types of basis sets: Gaussians have allowed a faster calculation of two electron integrals, and consequently an extension

of quantum chemistry towards larger systems, permitted also by a

great improvement of computer performances. At the present time,

the main goals of researchers are the implementation of calculations

for larger and larger systems, and also a better understanding of

excited states.

This Doctoral Thesis is devoted to the study of a type of functions, the Sturmian hydrogenic orbitals, which so far have received

very little attention in the eld of quantum chemistry. Hydrogenic

Sturmians are formally similar to the well-known hydrogenic orbitals, but their use has important and peculiar implications that

are worthwhile investigating. We have considered the applications

of Sturmians in ab initio quantum chemistry, without entering the

eld of density functional theory. The Thesis is structured in three

parts.

the properties of hydrogenic Sturmian orbitals.

In chapter 1 it is shown that there are dierent types of coordinates suitable for the solution of Sturmian Hydrogenic wave-

7

function in conguration space; consequently, there are different types of hydrogenic Sturmians in conguration space.

Symmetry properties and orthonormal transformations among

them are studied.

Chapter 2 deals with the properties of Sturmians in momentum space. In the reciprocal space, Sturmians are strictly

related to hyperspherical harmonics. This property is very

interesting by itself and also because it suggests the application of angular momentum techniques in quantum chemistry.

There are dierent types of hydrogenic Sturmians in momentum space; as in the previous chapter, Symmetry properties

and orthonormal transformations among them are studied.

The relationship between the two reciprocal spaces is also

discussed.

The second part of this thesis (Chapters 3,4 and 5) is dedicated to the applications of Sturmian basis sets in quantum

chemistry.

In chapter 3 the application of Sturmian orbitals as a basis set for atomic structure calculations is investigated, also

including the eect of external elds.

In chapter 4 there is a treatment of Sturmian formalism applied to one electron molecules according to the MO-LCAO

method.

Chapter 5 deals with an original method for exploiting Stur-

8

mians in a valence bond approach to the study of molecules.

The passage to momentum space is used in order to solve

some multi-center one-electron integrals

of PF5 molecule. The electronic ground state potential energy surface is obtained by density functional calculations.

Then, the nuclear rearrangement dynamics of the molecules

are studied by quantum techniques.

Chapter 1

Hydrogenic Elliptic Orbitals, Coulomb

Sturmian Sets and Recoupling

Coecients among Alternative Bases

Summary

The non-relativistic Schrodinger equation for the Coulomb problem is separable in four dierent coordinate systems in conguration

space: alternative sets of orbitals for the hydrogen-like atoms correspond to each of them and permit to obtain Sturmian sets, useful as

complete orthonormal expansion bases in atomic and molecular calculations. In this chapter the fundamental properties of the already

known hydrogenic orbitals (the familiar polar, the parabolic and the

rarely treated spheroidal sets) are resumed; then we discuss some

properties of the spheroelliptic orbitals, which have been so far practically ignored. We pay particular attention to the symmetries of

the dierent orbital sets and to the relationships between them, and

9

10

we order them in a complete scheme which exhibits passages from

one to the other through explicitly derived orthogonal transformations. Within this context we insert the study on the conservation

of parity in the passage from the polar set to the parabolic one. We

also show that - except for the spheroidal set - all alternatives for

hydrogenic wave functions induce irreducible representations of the

point group D2h , the `quaternion group'. This has relevance for the

discussion of connections between these sets and the corresponding

ones in momentum space, presented in Chapter 2.

1.1 Introduction

The Schrodinger equation for the hydrogen atom was solved in

the early days of quantum mechanics by using polar coordinates

(r; #; '). The other coordinate systems suitable for separating and

solving the equation are less known; each of them leads to hydrogenic orbitals with dierent properties. A systematic search on this

topic was completed in the 70's exploiting the relations between

separation of variables for dierential equations and Lie group theory [1,2]. In spite of the apparent simplicity of the hydrogen atom

as a physical system , its quantum-mechanical treatment turns out

to be wide and complicated; the reason can be found in its exceptional symmetry, which is the symmetry of the (hyper)-sphere

S 3 , embedded in a four-dimensional Euclidean space. Our interest

towards this study is due not only to the scientic quest for under-

11

standing properties of the only atom of the periodic table which

can be treated exactly by an analytical approach, but also to the

important aspect that the various types of orbitals are candidates

as basis sets for the numerical solution of other atomic and molecular systems, and are therefore basic building blocks for quantum

chemistry.

The physical quantum states for a hydrogenic atom with nuclear

charge Z are described by the wave functions which are solutions

of the Schrodinger equation:

(H^

E)

1 2

r

2

Z

r

=0

(1.1)

where r is the distance nucleus-electron. This is an exactly solvable two-body problem, at variance with all the other atoms of the

periodic table. The hydrogenic hamiltonian operator H^ has a discrete spectrum (bound states, negative E ) and a continuous one

(unbound states, positive E ), and one has to take both to get a

complete set. In view of diculties which arise when working with

continuous basis sets, it is better to associate a discrete set to the

solution of the quantum problem in Eq. (1.1). Such a complete set

of orbitals is called Coulomb Sturmian, the nomenclature originating from the fact that Eq. (1.1) is a Sturm-Liouville problem.

The quest for completeness lead many authors to introduce sets

which are closely related to usual orbitals, but for which completeness holds with no need of continuum states, an early example being

the "Natural Spin Orbitals" by Shull and Lowdin [3]. General Stur-

12

mian functions were introduced by Rotenberg [4, 5], starting from

the Schrodinger equation for the variable r in a radial-eld system

in the three dimensional physical space. The most important example is the Coulomb problem, for which Sturmian functions are

dened as solutions of the equation

"

1 d 2d

r

2r2 dr dr

l(l + 1)

+ E0

2r2

Zn

R (r) = 0

r n;l

(1.2)

number, a "reference" energy, to which it will be convenient in the

following to associate a "reference" momentum

p0 = ( 2E0 )1=2

(1.3)

0 and Rn;l (1) ! 0. Eq. (1.2), written in a.u., is very similar to

the radial part of the Schrodinger equation for the hydrogenic atom

separated in polar coordinates: the main dierence is that in the

latter the nuclear charge Z is xed a priori and only a discrete

spectrum of energies turns out to be allowed, while in the SturmLiouville equation the energy E0 is xed, and the "nuclear charge"

Zn is varied until the boundary conditions are fullled, generating

a complete set of Coulomb Sturmians, which are therefore the radial functions Rn;l (r) multiplied by the usual spherical harmonics

as angular functions: un;l;m(r; #; ') = Rn;l (r) Yl;m(#; ').

It can be veried that if for example E0 is 1=2, i.e. the energy of the ground state of hydrogen atom, then one has Z1 = 1

13

and u1;0;0(r; #; ') is the wave function for the orbital 1s; no other

un;l;m(r; #; ') corresponds to a physical wave function, but a complete set can be explicitly dened. Coulomb Sturmians obey a

peculiar orthonormality relation [6]:

Z

1

p

un;l;m(r; #; ')dr = 0 nn0 ll0 mm0

r

n

(1.4)

The number of allowed Zn is unlimited, thus there exists an innite number of un;l;m(r). Such innite set is complete, but n is

numerable: therefore there is no continuous spectrum, and this is

the fundamental feature of these sets [3, 6{9]:

X

n;l;m

r0 ) (# #0 ) (' '0 )

(1.5)

In the next section we will further discuss the apparent coincidence

and the dierences between Coulomb Sturmian eigenfunction sets

and the usual hydrogenic orbitals.

The hamiltonian in Eq. (1.1) can be easily formulated, by using

a Cartesian coordinate system centered on the nucleus, but it is

known that these coordinates lead to a non-separable dierential

equation. The problem of the separation of variables is ubiquitous

in quantum mechanics, because in the study of systems with many

degrees of freedom one tries to reduce the original multidimensional

problem in the hope of getting problems of lower dimensionality,

which are simple enough to be solved analytically or numerically,

14

and allowing us to better understand the physical process and to

refer to simpler cases. Separation of variables can be exact or only

approximate. Exact separation can be viewed as symmetry separation, since it is associated to geometrical and dynamical symmetries

of the system [10, 11]; this is the type of variable separation which

applies to the study of the hydrogen atom as a two-body problem

and thus will be under focus in this chapter. Symmetry separation

usually involves the introduction of separation constants to isolate

each variable, and for each of them one gets a dierential equation where only one degree of freedom appears. In other words, a

partial dierential equation becomes a set of (uncoupled) ordinary

dierential equations.

For most quantum systems, which are made of three or more

bodies, an approximate separation can be performed, based on the

assumption that the motion associated to a group of variables can

be treated as the other ones were frozen; the "fast" variables produce an eective potential for the motion of the "slow" variables,

which will have to be treated accordingly. The semiclassical nature

of this adiabatic separation procedure has been elucidated [12, 13].

The Born-Oppenheimer separation is an example, as well as the

hyperspherical approach to the few-body problem.

In the next sections, we will consider the four coordinate systems

which allow the exact separation of the Schrodinger equation. For

each coordinate system the properties of the corresponding Sturmian basis vary and the ranges of problems for which they are

15

appropriate basis sets dier accordingly.

Sturmian sets in conguration space have hyperspherical harmonics basis sets as their counterparts in momentum space. Care

will be taken to develop the treatment to prepare for the following

chapter, where hyperspherical symmetry is exploited in the momentum space framework. The correspondence is best understood

making reference to symmetry, and thus to group theory. The second order commuting operators which appear as constants of the

motion in the treatment of hydrogen atom in momentum space - our

next chapter will deal with the latter - are invariant with respect to

the inversion operation: as a consequence, momentum space Sturmians induce irreducible representations of the point group D2h [2]

(Schon
ies notation is used throughout this thesis, see Ref. [14]).

Thus, only conguration space Sturmians inducing irreducible representation of D2h have a counterpart in the momentum space corresponding to the same set of quantum numbers. For this reason

we pay special attention in the present chapter to the behaviour

of the conguration space Sturmians in the point group D2h . This

correspondence will be treated in the following chapter, where previous problems such as the Coulson's "intractability of spheroidal

orbitals" [15] will be shown to arise from the dierent behaviour of

commuting operators resulting from separation of variables in the

two reciprocal spaces with respect to inversion of parity.

Notations and properties of polar and parabolic Sturmians, having been recently discussed (and also extended to the general d-

16

dimensional hydrogen atom case) [16], are brie
y resumed in Sec. 2,

while in Sec. 3 we implement the requirement of parity conservation

in the orthogonal matrix which connects the two sets. Spheroidal

Sturmians are described in Sec. 4 (the corresponding hydrogenic

orbitals have been lucidly illustrated by Sung and Herschbach [17]).

Spheroelliptic Sturmians and their properties are introduced in Sec.

5, where their expansion coecients in terms of the other sets are

given as solutions of a three-term recursion relationship, which also

allows us to obtain the `missing label', i.e. the additional quantum

number characterizing the set (this is typical of elliptic coordinates

and basis sets, an ample variety of which will be encountered in

the next chapter). This work leads to the complete list of Coulomb

Sturmian sets and of the recoupling coecients among alternative

bases: the corresponding connection scheme will be exhibited in

the concluding Section.

The separation of variables in dierential equations can be associated to the algebraic structure described by the theory of continuous groups [1, 2, 10]. Therefore the Schrodinger equation for a

given system has to be discussed with reference to its dynamical

symmetries. The Coulomb potential is radial, i.e. it depends only

from the distance r between nucleus and electron, and therefore the

hydrogen atom has an evident spherical symmetry and the polar

17

coordinates (see g. 1a) are the most natural choice for solving eq.

(1.1). Writing the polar Sturmian as a product of a radial factor

Rn;l (r) and an angular factor Yl;m (#; ') enables us to separate the

coordinate r from the others. After introducing the separation constant l(l + 1), we obtain two dierential equations: the rst one is

eq. (1.2), and the second one

"

1 @

@

1 @2

sin #

+ 2

Y (#; ') = l(l + 1)Yl;m(#; ')

sin # @#

@#

sin # @'2 l;m

(1.6)

coincides with the equation for the free motion of a particle on

the surface of the three-dimensional sphere S 2 ; it is known that the

wave functions of that system are the spherical harmonics Yl;m (#; ') =

Nl;m Pljmj(cos #) eim' (Nl;m is the normalization factor [18]). The

explicit expression of the polar Coulomb Sturmians in conguration

space is:

"

#

l 1)! 1=2

2n[(n + l)!]3

(n

un;l;m(r; #; ') = (2p0 )3=2

(1.7)

l 2l+1

0 r) Ln l 1 (2p0 r) Yl;m(#; ')

p r (2p

0

where p0 =

2E0 , n = 1; 2; 3; : : :, l = 0; 1; : : : ; n 1 and l

m l; L2nl+1l 1 (2p0 r) is a Laguerre polynomial [19]. The use of p0

instead of the more traditional energy E0 serves to emphasize the

connection with the treatment of the same problem in momentum

space, which will be presented in the following chapter. It is important to stress that Eq. (1.7) also represents hydrogenic orbitals:

the dierence between orbitals and Sturmians is that in the former

18

in the latter p0 is a xed number and the nuclear charge Z can take

any value Zn according to the relationship Zn = p0 n. The Sturmians can be seen as satisfying the following eigenvalue equations, in

which ^l is the orbital angular momentum of the electron:

1 2 p20

r+2

2

^l2

np0

un;l;m(r) = 0

r

i

l(l + 1) un;l;m(r) = 0

(^lz m) un;l;m(r) = 0

(1.8)

(1.9)

(1.10)

In Eq. 1.8 the product np0 gives the "charge" Zn . To these three

relationships we add

P^ un;l;m(r) = un;l;m(r)

(1.11)

where P^ is the operator that performs the inversion of all the electronic coordinates with respect to the nucleus, and = ( 1)l .

The following real linear combination of polar orbitals are conveniently dened ( = 1):

(1.12)

all three Cartesian axes ( = 1, according to whether m is even

or odd):

C^2 (y ) un;l;jmj = un;l;jmj

(1.13)

(1.14)

19

Table 1 - Number of polar (Eq. 1.12) or spheroelliptic functions for

given l, and labels.

; !

l=1

2

3

4

5

6

...

even l

odd l

+1,+1

-1,+1

1

2

2

3

3

4

...

l=2 + 1

(l + 1)=2 (l

+1,-1

-1,-1

0

1

1

1

1

1

1

2

2

2

2

2

2

3

3

3

3

3

...

...

...

l=2

l=2

l=2

1)=2 (l + 1)=2 (l + 1)=2

P^ un;l;jmj = un;l;jmj

(1.15)

(1.16)

Therefore the functions un;l;jmj are seen to induce irreducible repre^ C^2 (x); C^2 (y ); C^2(z )g

sentations in the point group D2h = D2 Ci (D2 = fE;

^ P^ g). This is also known as the "quaternion group".

and Ci = fE;

For symmetry operations and groups, we use the notation of Ref.

[14]. Table 1 shows the number of un;l;jmj functions for given l;

and values.

The separation of variables in the Schrodinger equation written

in polar coordinates is always possible for the motion in any radial

eld. In the case of Coulomb eld, separation of variables is also

possible in parabolic coordinates (Fig. 1a).

These coordinates have two points of reference: one is on the

20

z

z

) /2

2

1+

P ()

( 1 2 ) /2

P ()

(+) A

(a)

( 1 2)

1/2

A (+)

(b)

x

=cost

Figure 1.1:

The part (a) of this gure shows polar and parabolic coordinates. The denition of the polar coordinates with respect to the cartesians

is x = r sin # cos '; y = r sin # sin '; z = r cos #. The relatioships of parabolic

coordinates with the cartesians and the polars are x = (1 2 )1=2 cos '; y =

(1 2 )1=2 sin '; z = 12 (1 2 a nd 1 = r(1 + cos #); 2 = r(1 cos #); ' = '.

The part (b) serves for the denition of spheroidal coordinates: = a+ b where

1 1 and = a b where 1 1. ' is the angle between the plane

ABP and a xed plane through AB; 0 ' < 2 . Therefore if the y axis is s

een as pointing downward in the plane of the drawing, ' is as in the part (a).

21

nucleus, and the other is at innite distance along a direction that

in Fig. 1a coincide with the z axis. The explicit expression for the

parabolic sturmians is, according to the notation in [20]:

1

2

3

0

p0p12 e

Lm(n+

n f[(+n+m 1)=2]![(n +m 1)=2]!g

m

p

1+

2

(1.17)

m

im'

m 1) (p0 1 ) L (n m 1) (p0 2 ) e

1

2

1 2 p20

r +2

2

np0

Un;;m (r) = 0

r

K^ z Un;;m (r) = 0

^lz m Un;;m (r) = 0

(1.18)

(1.19)

(1.20)

1; 2; 3;. . . , (n 1) m (n 1) and (n jmj 1)

(n jmj 1). For alternative notations for parabolic quantum

numbers and generalized Laguerre polynomials, and their relationships with the present ones, see Ref. [21]. In eq. (1.19) the operator

K^ z corresponds to the component along the z axis of the reduced

Runge-Lenz vector [2,22,23], which classically gives the direction of

the major axis of an elliptic orbit; it is a costant of the motion and

therefore commutes with the hamiltonian operator. The operator

K^ is dened as:

K^ =

1 ^

l p^

2

p^ ^l

Zr

=p0

r

(1.21)

22

The vectors K and l are orthogonal in classical mechanics, and for

^ = 0. Since ^l is invariant

the quantum mechanical operators ^l K

with respect to inversion, while p^ and r change sign, eq. (1.21)

^ also changes sign under inversion; thus K^z doesn't

implies that K

commute with P^ and the parabolic functions [Eq. (1.17)], being

eigenfunctions of K^ z , do not have a well dened parity. We will

come back to this point in the following section, both because this

is crucial in establishing relationships with the momentum space

treatment and also because for applications it is often useful to

have a basis of denite parity.

The trasformation matrix between the polar set jn; l; mi [Eq.

(1.7)] and the parabolic set jn; ; mi [Eq. (1.17)] has to conserve the

quantum numbers n and m, then it is made of blocks of dimension

n jmj because for xed n and m, there exist n jmj polar orbitals

and n jmj parabolic orbitals. Within a phase factor, the matrix

elements - which coincide with the overlaps of the functions of the

two sets - are particular Clebsch-Gordan (CG) coecients [18, 22,

24, 25] in which the two coupling vectors have the same modulus

[26]:

jn; l; mi

Pn jmj

= (n jmj 1)

( ) (n +m 1) cn;m

l; jn; ; mi

1

2

(1.22)

1); 2 + 2 2

2 + 2 j l; mi

This relationship shows that the connection between the polar and

parabolic basis can be seen as a change of coupling schemes [17],

^ ).

involving the angular momentum operators k^ = 12 (^l K

cn;m

l;

= h 21 (n

m ; 1 (n

1);

23

An alternative view of these matrix elements stems from the

Regge symmetry [25, 27] for the Clebsch-Gordan coecients:

h 12 (n 1); 12 (m ); 12 (n 1); 21 (m + )jl; mi =

h 12 (n + m 1); 2 ; 12 (n m 1); 2 jl; 0i

(1.23)

The last form (a Clebsch-Gordan coecient where the projection

of the orbital angular momentum is zero) suggests that can be

interpreted as a helicity quantum number [21]. Indeed the choice

of the reference frame for which the component of the orbital angular momentum vector ^l is zero amounts to change the quantization

axis on the plane of the orbit, where the Runge-Lenz vector lies.

This choice is reminiscent of analogous ones which occur in different contexts: we recall the transformation between space-xed

and body-xed frames in molecular collisions [28], the transformation between the Hund's cases (e) ! (c) in molecular spectroscopy

and atomic scattering [29, 30] and the passage between symmetric

and asymmetric coordinates in the hyperspherical treatment of the

three-body problem [31, 32].

In general, the CG coecients enjoy two basic three-term recurrence relationships with respect to angular momentum and to

the projection quantum numbers [33, 34]. For the CG coecients

in Eq. 1.22, we have with respect to l:

v

u

u

t

v

u

u [(n

[n2 l2 ][l2 m2 ] n;m

1)2 l2 ][l2 m2 ] n;m

t

cl 1; cn;m

+

cl+1; = 0

l;

(2l 1)(2l + 1)

(2l + 3)(2l + 1)

(1.24)

24

and with respect to :

1q 2

[n

4

l;+2 +

1 2

1

(n 1) + (m2 2 ) l(l + 1) cn;m

l; +

2

2

1q 2

[n (m + 1)2 ] [n2 (m + 1)] cn;m

l; 2 = 0

4

(1.25)

Eqs. 1.24 and 1.25 can be seen from a matricial point of view:

the CG coecients that appear there are eigenvectors of tridiagonal

matrices. Eq. 1.24 corresponds to the matrix representation of K^ z

by the set jn; l; mi, the eigenvalues being ; eq. 1.25 corresponds to

the matrix representation of ^l2 by the set jn; ; mi, the eigenvalues

being l(l + 1). Here we see a manifestation of properties which can

be viewed from the relationships between CG coecients and Hahn

polynomials of a discrete variable [35]. For these polynomials and

their duals, there is an exchange in the role of the discrete variable

and their degree, and Equations like (1.24) and (1.25) can be also

seen as the nite dierence equations respectively either in l or .

trasformation between polar and parabolic

orbitals

Let us consider explicitly, at given n and m values, the matrix

elements of ^l2 on the basis jn; ; mi: those on the row labeled by

are the coecients appearing in Eq. (1.25). We observe that such

25

a matrix is centrosymmetric (a matrix A of dimensions d d is

centrosymmetric if Aj;k = Ad+1 j;d+1 k ), implying the existence of

a simple similitude transformation which factorizes it in two blocks

[36]. Accordingly, the set jn; ; mi transforms into a new set of

eigenfunctions of the parity operator P^ , which commutes with ^l2 .

Block-diagonalization occurs because matrix elements of ^l2 between

functions which have opposite parity vanish. The explicit form of

the new basis of denite parity, which will turn out to be connected

by a simple relationship with the originary basis, can be obtained

by projecting out the even and odd components of the parabolic

Sturmians in Eq. (1.17).

As we can see from Figure 1, inverting the position vector r

of the electron amounts, in parabolic coordinates, to exchanging

1 and 2 and turning ' into ' + . By summing or subtracting

Un;;m (1 ; 2 ; ') and Un;;m (2 ; 1 ; ' + ), we get the even (U + ) and

the odd (U ) components of the latter ( = 1, as before):

1

U (1 ; 2 ; ') = p [Un;;m (1 ; 2 ; ') Un;;m (2 ; 1 ; ' + )] =

2

(1.26)

1

= p [Un;;m (1 ; 2 ; ') ( )m Un;;m (2 ; 1 ; ')] =

2

q

m

h

1

= p Nn;;m p0 1 2 e p

Lm(n+ m 1) (p0 1 )

2

i

Lm(n m 1) (p0 2 ) ( )m Lm(n m 1) (p0 1 )Lm(n+ m 1) (p0 2 ) eim'

0

1

2

1

2

1+

2

1

2

1

2

and Eq. (1.17). The comparison also shows that these denite-

26

parity parabolic orbitals are linear combinations of two orbitals

which have opposite values of :

1

Un; jj;m = jn; ; m; i = p [Un;;m ( )m Un;

2

;m ]

(1.27)

be eigenfunctions of H^ and ^lz , but they are so now also for K^ z2 and

P^ (and not for K^ z ):

P^ Un; jj;m = Un; jj;m

(1.28)

(1.29)

and P^ commute.

Having dened the parity basis set, we derive the matrix elements Cl;n;m;

jj for its transformation into the polar set:

jn; l; mi =

n X

jmj 1

=0 or 1

( ) (n +m 1) Cl;n;m;

jj jn; ; m; i

1

2

(1.30)

where the step of the sum over is two units; it starts from 0 or 1,

according to whether n jmj 1 is even or odd: indeed, in the ket

jn; ; m; i of dened parity, can only be positive or zero. The

desired orthonormal transformation matrix has to be factorized in

two blocks distinguished by the sign of the parity , at xed values

of n and m. We have

1 + ( )l n;m

q

Cl;n;m;

=

cl;jj

jj

2(1 + ;0 )

(1.31)

27

For each parity, columns are now labeled by jj and , instead of

as in Eq. (1.22), and the quantities Cl;n;m;

jj are combinations of CG

coecients in Eq. (1.22) which dier only for the sign of :

Cl;n;m;

jj =

h

i

1

m cn;m

cn;m

+

(

)

l;

l;

2(1 + ;0 )

(1.32)

p

= 1 ( = +1). For 6= 0, it takes the value 2cn;m

l;jj , and in

the particular case = 0, it is simply the CG coecient cn;m

l;=0 .

The matrix elements cn;m

l;=0 constitute an eigenvector of parity =

( 1)m ; accordingly, when l and m have opposite parity, they are

zero.

A parity factor which is analogue to the one in Eq. 1.31 had

already appeared in the literature in dierent contexts, for example, in the study of the passages among the various angular momentum coupling schemes in the quantum mechanical treatment of

molecular [28] and open-shell atomic [29] collisions. Let us show an

example; for n = 4 and m = 0 we have:

0

B

B

B

B

@

u4;0;0

u4;1;0

u4;2;0

u4;3;0

C

C

C

C

A

B

B

B

B

B

@

3

2

1

2

1

2

q

1

2

q

1

5

1

5

1

2

q

1 1

2 5

1

2

q

3 1

2 5

1

q2

1 1

2 5

1

2q

3 1

2 5

1

q2

3 1

2 5

1

q2

1 1

2 5

10

CB

CB

CB

CB

C@

A

U4; 3;0

U4; 1;0

U4;1;0

U4;3;0

1

C

C

C

C

A

(1.33)

28

Block-diagonalizing according to the conservation of parity, one has:

0

B

B

B

B

@

u4;1;0

u4;3;0

u4;0;0

u4;2;0

1

C

C

C

C

A

B

B

B

B

B

B

@

3q 101

0

0

1

10

1

q 10

3 101

0

0

0

0

p1

2

p1

2

0

0

p1

2

p1

2

0

C

CB

CB

CB

CB

C@

A

U4;3;0

U4;1;0

U4+;1;0

U4+;3;0

1

C

C

C

C

A

(1.34)

Eq. (1.31) denes analogues of the CG coecients which conserve the parity; we will refer to them as parity-conserving ClebschGordan coecients (pCG). In the following we will show how to

work out the three-term recurrence relationships enjoyed by pCG

coecients. Indeed, the eigenvectors of the matrix of K^ z2 in the

basis jn; l; mi are eigenfunctions also of H^ and ^lz : in fact since

[K^ z2 ; H^ ] = [K^ z2 ; ^lz ] = 0, the matrix elements of functions which differ in n and/or m are zero, and n and m are preserved as good

quantum numbers. Therefore, the matrix is diagonalized by the

coecients of the orthogonal transformation between jn; l; mi and

jn; ; m; i: those coecients are exactly pCG-coecients. We will

see that the matrix is tridiagonal, and therefore the pCG coecients

enjoy a three-term recurrence relationship.

As we have seen, [K^ z2 ; P^ ] = 0, and the parity of jn; l; mi is ( 1)l ,

so we expect that only matrix elements hn; l0 ; mjK^ z2 jn; l; mi with l

and l0 having the same parity can be dierent from zero. This

implies that the matrix is factorized in two blocks, for even and

29

odd l. In the l-th row only three elements are dierent from zero:

m ][n (l+1) ]

[l m ][n l ]

hn; l; m j K^ z2 j n; l; mi = [(l+1)(2l+1)(2

+

l+3)

(2l 1)(2l+1)

2

hn; l; m j K^ z2 j n; l +2; mi = (2l1+3) [n (l+2) ][(l+2) (2l+1)(2

l+5)

r

[

n

(

l

1)

][(

l

1)

m

][

n

l ][l m ]

hn; l; m j K^ z2 j n; l 2; mi = (2l1 1)

(2l 3)(2l+1)

(1.35)

Consequently, we have a recurrence relationship among the Cl;n;m;

jj

which dier by two units in the value of l:

v

u

u

t

[n2

m]

2

Cl 2;jj +(1.36)

(2l 3)(2l 1)2 (2l + 1)

(

)

[(l + 1)2 m2 ] [n2 (l + 1)2 ] [l2 m2 ] [n2 l2 ]

2

+

Cl;n;m;

jj +

(2l + 1)(2l + 3)

(2l 1)(2l + 1)

v

u 2

u [n

(l + 2)2 ] [(l + 2)2 m2 ] [n2 (l + 1)2 ] [(l + 1)2 m2 ] n;m;

t

Cl+2;jj = 0

(2l + 1)(2l + 3)2 (2l + 5)

Eq. (1.36) relates the coecients which belong to the same parity

block in the transformation matrix between the basis sets jn; l; mi

and jn; ; m; i.

In order to work out the second recurrence relationship for the

pCG coecients, we have to consider the matrix of ^l2 in the basis

jn; ; m; i. Since [^l2; P^ ] = 0, only the matrix elements between

functions of the same parity can dier from zero, so we have again

a factorization in two blocks. The eect of ^l2 on jn; ; m; i is

identical to its eect on jn; ; mi, thus the recurrence over of the

pCG coecients

1q 2

[n (m + 1)2 ] [n2 (m + 1)2 ] Cl;n;m;

j 2j +

4

(l

30

1

1 2

(n 1) + (m2 2 ) l(l + 1) Cl;n;m;

jj +

2

2

(m + + 1)2 ] [n2 (m 1)2 ] Cl;n;m;

j+2j = 0 (1.37)

1q 2

[n

4

is identical to the recurrence for the CG (Eq. 1.25), apart from the

range of .

Finally, we complete this section by building-up explicitly real

parabolic orbitals which enjoy the symmetry properties of the group

D2h : they are

Un;;jj;jmj = jn; ; m; ; i = (2i 1 ) 1=2 Un; jj;m Un; jj;

(1.38)

ducible representations for the group D2h , being eigenfunctions of

the following operators ( = 1 corresponds to even or odd m):

C^2 (y ) Un;;jj;jmj = Un;;jj;jmj

C^2 (z ) Un;;jj;jmj = Un;;jj;jmj

P^ Un;;jj;jmj = Un;;jj;jmj

(1.39)

(1.40)

(1.41)

(1.42)

For xed n and jmj, there exist n jmj functions of type Un;;jj;jmj.

Table 2 indicates how many of these functions there are for each

couple of and labels at a given n jmj value. From the fact

that eq. (1.22) is invariant with respect to the sign of m, it follows that the coecients of the transformation between jn; l; m; i

and jn; ; m; ; i coincide with the pCG coecients, i.e. with the

coecients of the transformation between jn; l; mi and jn; ; m; i.

31

Table 2 - Number of D2h parabolic functions (Eq. 1.38) for given

and labels and n jmj xed.

; !

even m

odd m

+1,+1

-1,+1

(n

jmj)=2 (n jmj)=2

+1,-1

(n

0

jmj)=2 (n

-1,-1

0

jmj)=2

A basic study of the hydrogen atom in spheroidal coordinates (Fig.

1b) is due to Coulson and collaborators [15, 37]. This two-center

coordinate system is very suitable for studying the motion of the

electron in H+2 within the Born-Oppenheimer approximation, because it renders the Schrodinger equation separable, though not

analytically solvable. In this way, "diatomic orbitals" - i.e. orbitals

for one electron between two nuclei - can be computed [38], and also

exploited for quantum calculations on two-electron problems [39].

In the case of hydrogen atom, one of the two centers coincides with

the nucleus and the other is set at a distance along a reference

axis. A brilliant exposition, whose spirit we follow, concerning both

H and H+2 can be found in Ref. [22]. The spheroidal orbitals are the

best zero-order functions to treat the hydrogen atom perturbed by

a point charge [40]. Analytical solutions for an electron interacting with two xed nucleus are known only for special values of the

internuclear distance and of the ratio of nuclear charge [37]. More

recent applications are cited in Refs. [17, 41, 42], and Ref. [43] is a

32

monograph on spheroidal functions.

In order to solve the Coulomb problem in spheroidal coordinates one writes the spheroidal Sturmians T (; ; ') as a product

( ) N ( )('), and introduces two separation constants, m2 e f .

Dening

p

Z

E0 1=2

= 0 = n

2

2

2n

we one can write the separated equations as:

d2

2

2 = m (1.43)

d'

"

#

"

#

d

d

m2

2

2

2

(1 )

+ f + 2n

= 0 (1.44)

d

d

1 2

The equation in is formally identical to the one in , but the

interval of denition of the variable is dierent (see Fig. 1a). Eq.

(1.43) also occurred in the separation in the polar variables # and

' (see Eq. 1.6); its normalized solutions are again (') = p12 eim' ,

and the T (; ; ') are eigenfunctions of ^lz .

Let us consider Eq. (1.44). Since for ! 1 the asymptotic

solution is e , we demand for the unknown function ( ) the

form:

nX1

( ) = e

cl Pljmj( )

(1.45)

l=jmj

the variability interval is [1; 1[, not [ 1; 1]. In order to calculate

the unknown coecients of Eq. (1.45), we have to put it in Eq.

(1.44) and after some passages omitted for brevity, taking into account some properties of the Pljmj( ) [19,44], a three-term recurrence

33

relationship for the cl is obtained [17, 22]:

(n + l + 1)(l + m + 1)

(n l)(m l) f + 2 l(l + 1)

+cl

cl+1

=0

(2l 1)

2

(2l + 3)

(1.46)

This amounts to say that, after xing n and jmj, it is necessary to

diagonalize a tridiagonal matrix of order n jmj to get the n jmj

spheroidal orbitals; the eigenvalues are the separation constants

f associated to each orbital. As a consequence, at variance with

what happens for the polar and parabolic basis sets, neither the

spheroidal eigenfunctions nor the eigenvalues f can be written as

a "closed" expression. Symmetrizing the recurrence relationship of

the cl (see Appendix) one has [22]:

cl 1

v

u

u

t

h

[n2 l2 ][l2 m2 ]

gl 1 + l(l + 1) f

(2l 1)(2l + 1)

2 gl +

v

u

u

t

gl+1 = 0

(1.47)

(2l + 3)(2l + 1)

Comparison with Eq. (1.24) shows that Eq. (1.47) is exactly what

one would get when solving the equation

2

(^l2 + 2K^ z ) = (f + 2 )

by expanding

(1.48)

=

nX1

l=jmj

gl jn; l; mi

orbitals means to nd eigenfunctions of the operator ^l2 + 2K^ z ,

34

besides obviously those of H^ and ^lz . The classical observable which

corresponds to the former operator is a constant of the motion in

the case of a two-centre Coulomb potential [45].

We list the eigenvalue equations which completely characterize

the spheroidal basis:

!

1 2 p20 np0

r + 2 r Tn;f;m (r) = 0

n = 1; 2; 3 : : : (1.49)

2

h

i

(^l2 + 2K^ z ) (f + 2 ) Tn;f;m (r) = 0

(1.50)

^lz m Tn;f;m (r) = 0

jmj = 0; 1; : : : ; n 1(1.51)

So, in order to obtain spheroidal orbitals without solving Eq. (1.44)

we can calculate the coecients of the expansion of the unknown

functions in an appropriate basis, by diagonalizing the matrix of

the operator ^l2 + 2K^ z in such a basis. Looking at this operator,

one understands how spheroidal orbitals are related to those we

have encountered before. As the distance tends to zero, does

too, therefore the operator becomes ^l2 , which is associated to the

jn; l; mi basis: as ! 0 the jn; f; mi set coincides with the jn; l; mi

set. On the other hand, as the distance between the two centers

goes to innity, the contribution from K^ z becomes dominant, thus

the jn; f; mi coincide with the jn; ; mi. One could work out the

same result by a more complicated study of the asymptotic limits

of the functions jn; f; mi [37]. Considering the eigenvalues (f + 2 ),

what we have just said implies that

lim (f + 2 ) = l(l + 1)

!0

and

lim

!1

f + 2

=

2

(1.52)

35

This conrms the role of spheroidal coordinates as a bridge between

the parabolic and the polar coordinates [17].

Eq. (1.47) allows the determination of the coecients of the

expansion of the basis jn; f; mi by the basis jn; l; mi; we propose

another way to get the jn; f; mi, calculating the coecients of their

expansion in parabolic orbitals jn; ; mi:

Tn;f;m (r) =

n X

jmj 1

= (n jmj 1)

hn;m

f; Un;;m (r)

(1.53)

f; are the elements of the eigenvectors which

diagonalize the matrix of ^l2 + 2K^ z on the basis jn; ; mi. Such

a matrix consists of blocks of dimension n jmj, where parabolic

functions having the same n and m interact; in fact the matrix

elements of two functions jn; ; mi that dier for n and/or m are

zero for the non-combination theorem, since ^l2 + 2K^ z commutes

with H^ and ^lz . In the -th row of the matrix, only three elements

are dierent from zero:

hn; ; m j ^l2 + 2K^ z j n; 2; mi =

1 2

[n (m + 1)2 ] [n2 (m + 1)]

4

hn; ; m j ^l2 + 2K^ z j n; ; mi =

i

1h 2

(n 1) + (m2 2 ) + 2

2

hn; ; m j ^l2 + 2K^ z j n; +2; mi =

1q 2

[n (m + + 1)2 ] [n2 (m 1)2 ]

4

(1.54)

(1.55)

(1.56)

36

Thus the coecients in Eq. (1.53) satisfy a three terms recurrence:

1q 2

[n (m + 1)2 ] [n2 (m + 1)] hn;m

f; 2 +

4

1 2

1

(n 1) + (m2 2 ) + 2 (f + 2 ) hn;m

f; +

2

2

1q 2

[n (m + + 1)2 ] [n2 (m 1)2 ] hn;m

f;+2 = 0 (1.57)

4

of the coecients cn;m

l; , because the matrix of the eigenvectors tends

to the trasformation matrix between jn; l; mi and jn; ; mi; in the

opposite limit the matrix elements in Eqs. (1.54) and (1.56) become

negligible with respect to the one in Eq. (1.55), since the latter

contains ; i.e., the basis jn; ; mi tends to diagonalize ^l2 + 2K^ z

when gets larger and larger.

The operator ^l2 +2K^ z can be seen, in the neighbourhood of its

asymptots, as a sum of a main part and a small perturbation: for

small the perturbation is 2K^ z , and spheroidal functions spring

from the eect of such perturbation on the zero-approximation

functions jn; l; mi ; on the other hand, when is large, the perturbation is ^l2 , and the jn; f; mi diers very little from the zeroapproximation functions jn; ; mi. Then we are able to use a perturbation approach at both of the extremes of our problem. For

example, for small the second-order formula for the eigenvalues

stemming from the perturbation of a level jn; l; mi is, by applying

the Rayleigh-Schrodinger Perturbation Theory [23]:

(f + 2 )[2]

l =

(1.58)

37

= l(l+1) 42

"

2(l + 1) (2l + 3)(2l + 1)

1 [n2 l2 ][l2 m2 ]

2l (2l 1)(2l + 1)

v

u

u

t

un;l+1;m+

(l + 1)

(2l + 3)(2l + 1)

(1.59)

v

u 2

u [n l2 ][l2 m2 ]

u

+ t

l (2l 1)(2l + 1) n;l 1;m

(Tn;f;m )[1]

l = un;l;m

on the parabolic eigenstates; the eigenvalues are found to be

(f + 2 )[2]

=

1

2 + (n2

2

1

1) + (m2

2

2 ) +

2

(n

8

(1.60)

2 + m2

1)

(Tn;f;m )[1]

=

1q 2

= Un;;m

[n (m + + 1)2 ] [n2 (m 1)2 ] Un;+2;m

8

1q

+ [n2 (m + 1)2 ] [n2 (m + 1)2 ] Un; 2;m (1.61)

8

Fig. 2 illustrates an application of these formulas to the approximation of the eigenvalues f for the case n = 5; m = 1. It is seen that

increasing the quantum number f , the approximation improves on

both extremes, encouraging its use for Rydberg states.

(f+ )/(2+n)

38

-2

-2

/4

arctan

Figure 1.2:

theory at both sides for the case n = 5; m = 1. The continuous lines show

^ z . The

the dependence on of the eigenvalues f of the operator ^l2 + 2K

approximations t o f calculated by perturbation theory are shown by dashed

lines.

/2

39

Besides the familiar spherical harmonics Yl;m (#; '), there exists a

dierent set of functions which solves the Schrodinger equation for

free motion on the S 2 sphere. We will call these functions elliptic harmonics since, as we will see soon, they arise from the

parametrization of the sphere by elliptic coordinates (referred to

also as "conical", e.g. in Ref. [20]) and Jacobi elliptic functions [19]

appear in their study. From a group-theoretical point of view,

there are two dierent function sets which induce irreducible representations of the continuous group of three-dimensional rotations

O(3) [1]. The close relationship between the hydrogen atom theory and the sphere S 2 (see the beginning of Section 2) implies that

elliptic harmonics can be used for building up a new type of hydrogen orbitals, which we will call spheroelliptic according to Ref. [2].

They are given as the product of the radial part of Eq. (1.7) and an

elliptic harmonic. There exist alternative equivalent parametrizations which render the motion on S 2 separable, and lead to elliptic

harmonics. One of them is [1]:

k2 + k02 = 1;

0 k 1;

0 k0 1

(1.62)

We see that Jacobi elliptic functions cn,sn and dn [19] appear. They

contain a continuous parameter (k or k0 ), called modulus, which can

assume any value between zero and one. Useful is consideration of

the modular angle , dened as sin = k [46] which can be put into

40

relationship with the distance between the "foci" of the ellipses (see

Fig. 3).

The parametrization in Eq. (1.62) leads to the elliptic harmonics:

(1.63)

where Ml;

e equations in Jacobian form

l;

[1]; l and are the quantum numbers which characterize these

k (; ) depends parametrically on k , so it has

harmonics. The Yl;

one degree of freedom more than the spherical harmonics.

The discussion in the previous Section demonstrates that it is

not necessary to solve explicitly the Schrodinger equation in order

to obtain the basis corresponding to a given parametrization: one

can calculate the coecients of the expansion of the unknown wavefunction on a suitable known basis. To do that, one has to know

the set of operators which characterize the unknown basis; for the

k ) [1]:

elliptic harmonics, they are (jl; i = Yl;

^l2

l(l + 1) jl; i = 0

E^ jl; i = 0

(1.64)

(1.65)

harmonics jl; mi, because they are solutions for the same physical

problem, and are both eigenfunctions of ^l2 . In the transformation

between the two basis sets the quantum number l is conserved,

thus the transformation matrix is factorized in blocks of dimension

41

k =1.00

= /2

y

x

z

k =0.866

= /3

y

x

z

k =0.707

= /4

y

x

z

k =0.500

= /6

y

x

z

k =0.00

= 0.00

Figure 1.3:

y

x

panels: various values for the modulus k and the corresponding modular angle

(Sec. 5) are given. In each closed curve on the surface of a sphere, one elliptic

coordinate is xed and the other coordinate is allowed to vary in its interval

of denition. At the limiting values of the modulus, spheroelliptic coordinates

are seen to coincide with the polar ones, as we expected. It is also seen that

the modular angle is in relationship with the distance between the foci of

the ellipses. On the right panels, the spheroelliptic Sturmian jl = 2; 1 ; =

+1; = +1i is represented for dierent values of k . One can see the gradual

passage from the dz2 to the dy2 z2 orbital.

42

2l + 1:

jl; i =

l

X

m= l

xl;m jl; mi

(1.66)

the basis jl; mi, one sees that the transformation coecients obey

the following three-term recurrence [1]:

Am 2 xl;m 2 + (Bm

) xl;m + Am xl;m+2 = 0

(1.67)

where

n

o1=2

1

(1 k02 ) (l m)[l2 (m + 1)2 ](l + m + 2)

4

h

i

1

= (1 + k02 ) l(l + 1) m2

2

Am =

Bm

one is that it relates coecients for which m has the same parity.

In other words Eq. 1.67 corresponds to a matrix factorized in two

blocks corresponding to even and odd m, thus some jl; i are linear

combinations of jl; mi with even m, while others are linear combinations of jl; mi with odd m. Along a line already pursued in Secs.

2 and 3, we also exploit a second less evident symmetry property,

namely that the matrix is centrosymmetric, so it can be further

factorized in two blocks [36]; this amounts to changing the basis

set from jl; mi to jl; m; i = p12 (jl; mi jl; mi) [compare with the

angular part of eq. (1.12)]. All this means that the jl; i can be

labeled by two further quantum numbers ( = 1 and = 1),

respectively associated with the parity of m ( = 1) and with the

43

relationship between xl;m and xl; m : xl;m = xl; m . From now

on, we will represent the elliptic harmonics by the ket jl; ; ; i.

Indicating the re
ection operators with respect to the planes

yz and xz as X^ and Y^ , one has X^ jl; mi = jl; mi and Y^ jl; mi =

( )m jl; mi. As a consequence, one has: X^ jl; ; ; i = jl; ; ; i

and X^ Y^ jl; ; ; i = jl; ; ; i. The value of the parameter k (or

k0 ) aects , not the other quantum numbers, therefore the symmetry with respect to the re
ection planes is not altered by varying

k (or k0 ). The spheroelliptic orbitals induce irreducible representations of the group D2h [47] [ = ( 1)l ]:

C^2 (y ) jl; ; ; i = jl; ; ; si

C^2 (z ) jl; ; ; i = jl; ; ; si

P^ jl; ; ; i = jl; ; ; si

(1.68)

(1.69)

(1.70)

(1.71)

harmonics coincide with simpler functions. As k0 ! 0, one has

E^ ! ^lx2 , then has to tend to m002 : the jl; ; ; i coincide with the

linear combination of spherical harmonics p12 (jl; m00 ijl; m00 i) for

which the quantization axis is x. Thus the matrix elements of the

transformation between the latter functions and the jl; mi fulll a

recurrence which is the limit of Eq. (1.67) as k0 ! 0; in this limit,

the eigenvalue becomes m002 and the eigenvectors can be identied

44

with suitable linear combinations of Wigner rotation functions [25]:

i

o1=2

1 nh 2

l (m 1)2 (l m + 2)(l + m)

4

Dml 2;m00 (0; ; ) Dml 2; m00 (0; ; ) +

2 2

2 2

i

1h

2

l(l + 1) m

m002

2

l

l

Dm;m00 (0; ; ) Dm; m00 (0; ; ) +

2 2

2 2

i

o1=2

1 nh 2

l (m + 1)2 (l m)(l + m + 2)

4

Dml +2;m00 (0; ; ) Dml +2; m00 (0; ; ) = 0

2 2

2 2

(1.72)

combining E^ and ^l2 one sees that the jl; ; ; i become eigenfunctions of ^lz2 ; they coincide with spherical harmonics quantized on the

z axis, namely jl; m; i = p12 (jl; mi jl; mi). Indeed, in this limit

the matrix of E^ on the basis jl; mi is diagonal.

Looking at the two limits of the operator E^ , one might try to

associate it to a rotation of the quantization axis by =2. However,

the operator describing the rotation by an angle is sin ^lx +cos ^lz .

Its matrix in the basis jl; mi is tridiagonal, and therefore the elements of the matrix that rotates the jl; mi by radians from the z

axis towards to x axis enjoy a three-term recurrence:

q

1

sin (l + m)(l

2

q

1

+ sin (l m)(l + m + 1) dlm+1;m00 ( ) =(1.73)

0

2

45

where we have explicitly made the identication with Wigner reduced d-matrix elements for which eq. (1.73) is a well-known property [25]. Comparing Eqs. (1.73) and (1.67) we can see that they

are not equivalent, and consequently one cannot associate a variation of k0 with a rotation of the quantization axis. To conrm this,

we note that for any value of k0 any function jl; ; ; i maintains

its symmetry with respect to the re
ection on xed planes ( and

are not aected by variation of k0 ), and this would not be possible if

the variation of k0 were associated to a rotation of the quantization

axis.

The reasonings about the relationship between spherical and elliptic harmonics can be extended to the corresponding parametrizations. In other words, the Jacobi elliptic functions must tend - as

the modulus takes limiting values - to the ordinary circular functions. Indeed the function sn(; k) can be dened as sn(; k)

sin ' where ' is given by [19]:

Z '

1

d

0 (1 k2 sin2 )1=2

(1.74)

!0 '

For k ! 0, the integrand function tends to one, therefore k=

!0 sin . In Figure 3 we show a representation of the

and sn(; k) k=

spheroelliptic coordinates on the surface of a sphere, for dierent

values of the modulus.

In order to clarify some of the previous concepts, it will be useful

to show an example concerning elliptic harmonics: the case l = 2

will be considered [1]. The elements of the matrix in eq. (1.75) are

46

;k0 = hl = 2; m j^

2

02 l2 jl = 2; mb i, where 2 ma ; mb 2:

Eml=2a ;m

a lx + k ^

y

b

El;k0 =

(1.75)

1

6

02

0

0

(1 + k02 )

0

2 (1 k )

C

B

5

3

0

2

0

2

C

B

0 p 2 (1 + k )

0

(1 k ) p 0

2

C

B

B

6 (1 k02 ) C

02 )

02 ) 6

C

B (1

0

3(1

+

k

0

k

2

2

C

B

3

5

C

B

0

2

0

2

0

(1

k

)

0

(1

+

k

)

0

A

@

2

2

p

6 (1 k02 )

02 )

0

(1

+

k

0

0

2

By appropriately changing the order of rows and columns it is easy

to show that this matrix if made of two blocks, which correspond to

the symmetry classes = 1. Moreover the matrix is centrosymmetric, thus using as a basis the harmonics jl; m; i we get a further

factorization [36]:

J 1El;k0 J =

(1.76)

0

(1 + k02 )

0

3(1 k02 )

0

0

B

C

0

2

B

C

0

(4 + k )

0

0

0

B p

C

B

C

0

2

0

2

B

C

3(1

k

)

0

3(1

+

k

)

0

0

B

C

0

2

B

C

0

0

0

(1

+

k

)

0

@

A

0

0

0

0

(1 + 4k02 )

where

0

1

1 0 0

1 0

B

C

B 0 1

C

0

0

1

B

C

p

1 B

J = p2 BB 0 0 2 0 0 CCC

(1.77)

B 0 1

C

0 0 1 A

@

1 0 0 1 0

Therefore the matrix is factorized in four blocks (three 1x1 and one

2x2) corresponding to the four symmetry classes ( = 1; = 1)

of the elliptic harmonics.

47

Note that one can follow a more straightforward procedure by

directly calculating the matrix of E^ on the basis jl; m; i, instead of

jl; mi: a recurrence relationship identical to Eq.(1.67) is obtained,

except for the matrix element Bm=1; =1 which now reads

1

4 (1

(1.78)

k02 + 1)1=2 ]

p

j2; 1;2; +1; +1i = ( 3=2)(1 k0 2)(k04 k02 + 1) 1=4

[2(k04 k02 + 1)1=2 (1 + k02 )] 1=2

"

#

(1 + k02 ) 2(k04 k02 + 1)1=2

p

(j2; 2i + j2; 2i)

j2; 0i +

02

6(1 k )

3 = 4 + k02

4 = 1 + k02

5 = 1 + 4k02

j2; 4; 1; +1i = p12 (j2; 2i j2; 2i) = dxy

j2; 5; 1; 1i = p12 (j2; 1i j2; 1i) = dyz

to their standard denition [48]. The right panel in Fig. 3 refers

to the orbital j2; 1 ; +1; +1i in the above formulas. Varying k0 its

shape varies too, but the symmetries with respect to the planes

are conserved. On the formula for 1 , we see that it tends to 6 as

k02 ! 1, as it should since the corresponding eigenfunction tends

to jl = 2; m2 = 0i, which is the harmonic dz :

2

l(l + 1) m2 = 6 0 = 6

48

. As k02 ! 0, 1 ! 4, the corresponding eigenfunction is indeed a

harmonic dy z (m002 = 4), i.e. the equivalent of dx y , but taking

x instead of z as the quantization axis.

For the case l = 3 (a 7x7 matrix), the -symmetry (even and

odd m) and the -symmetry lead to a factorization into four blocks:

one is 1x1 and three are 2x2. For higher l's, three-dimensional or

larger blocks may result from the factorization. In Table 1 we show

the number of functions in each of the four symmetry classes for

the lower values of l.

2

1.6 Conclusion

In this chapter we have resumed the most important features of

polar, parabolic and spheroidal hydrogenic orbitals, especially emphasizing their use as Sturmian basis sets; we have also studied

their behavior with respect to the inversion and in general to the

symmetry operations of the point group D2h . Spheroidal Sturmians do not belong to the D2h point group, while the other types of

Sturmians are found to induce irreducible representations of that

group, or to do that after an easy transformation, as the one in

Eq. (1.38). Within this context we have given [eq. (1.31)] a general expression for the coecients which conserve the parity in the

transformation between the polar and the parabolic sets. Then we

have presented the features of a lesser known set, the spheroelliptic

one.

49

20

15

10

5

1

0.2

0.4

0.6

Figure 1.4:

0.8

0.2

0.4

0.6

0.8

panels: various values for the modulus k and the corresponding modular angle

(Sec. 5) are given. In each closed curve on the surface of a sphere, one elliptic

coordinate is xed and the other coordinate is allowed to vary in its interval

of denition. At the limiting values of the modulus, spheroelliptic coordinates

are seen to coincide with the polar ones, as we expected. It is also seen that

the modular angle is in relationship with the distance between the foci of

the ellipses. On the right panels, the spheroelliptic Sturmian jl = 2; 1 ; =

+1; = +1i is represented for dierent values of k . One can see the gradual

passage from the dz2 to the dy2 z2 orbital.

50

,,

|m >

|lm>

|lm>

|lm>

,

|m >

|m >

|m,, >

|fm>

|lm>

,,

|l >

,

|l >

|lm>

|fm>

|m,>

Figure 1.5:

|l >

|lm>

|fm>

|m >

shown in the upper panel. The quantum number n has not been indicated

explicitely since it is conserved in all transformations. The functions of type

jn; l; mi (polar Sturmians) correspond to eq. (1.7): they can be expressed as

products of a Laguerre polynomial and a spherical harmonic, and are eigen^ ^l2 ; ^lz . The functions of type jn; ; mi (parabolic Sturmians)

functions of H;

correspond to eq. (1.17): they can be expressed as products of two Laguerre

^ K

^ z ; ^lz .

polynomials and an exponential function, and are eigenfunctions of H;

In the lower panel we have inserted also spheroidal and spheroelliptic Sturmians. The functions of type jn; f; mi (spheroidal Sturmians) are described

in Section 4: they can be expressed as products of two spheroidal Coulomb

^ ^l2 + 2K

^ z ; ^lz . The

functions and an exponential, and are eigenfunctions of H;

functions of type jn; l; i (spheroelliptic Sturmians) are described in Section 5:

they can be expressed as products of a Laguerre polynomial and two Lame

^ ^l2 ; ^lx2 + k 02 ^ly2 .

polynomials, and are eigenfunctions of H;

51

We have paid a great deal of attention to the relationships and

the recoupling coecients among the alternative basis sets. Thus,

now we are able to show (Fig. 5) a complete connection scheme for

alternative hydrogenic Sturmians in conguration space, including

the orthogonal transformations among them. Each connection line

in these gures corresponds to an orthogonal transformation between two alternative basis sets at the extremes of the line. Dotted

lines are associated to the Wigner rotation matrices [18, 24] which

perform the change of the polar axis:

jn; l; mi =

l

X

l

Dm;m

0 (0; ; ) jn; l; m0 i

2 2

m0 = l

sets [Eq. (1.22)]. Dashed lines correspond the transformations of

type

jn; f; mi =

nX1

l=jmj

gln;m jn; l; mi

passage between jn; ; mi and jn; f; mi functions, described by Eqs.

(1.53) and (1.57). Double lines correspond to the transformation

between polar Sturmians, such as jn; l; mi and spheroelliptic Sturmians jn; l; ; ; si = Rn;l (r)jl; ; ; i, described by Eqs. (1.66) and

(1.67). An orthonormal transformation between any two Coulomb

Sturmian sets can be performed following the corresponding path

on our graphs.

In the next chapter we will extend the study of hydrogen atom

52

in momentum space presented in ref. [49], in order to consider also

elliptic Sturmians and to implement the conservation of parity in

the transformations between any alternative basis sets. We will

compare the results with the ones of the present chapter, nding

analogies and dierences of the treatment of hydrogen atom in the

two reciprocal spaces.

recurrence relationships

Let us consider a secular equation c 1Fc = f in the case that F

is tridiagonal. The elements of the kth eigevector of F fulll the

system:

8

>

>

>

>

>

<

>

>

>

>

>

:

c1;k F2;1 + c2;k (F2;2 fk ) + c3;k F2;3

...

...

=0

=0

fk ) = 0

(1.79)

Therefore the elements of eigenvectors of a tridiagonal matrix enjoy

a three-term recurrence relationship: ci 1;k Fi;i 1 + ci;k (Fi;i fk ) +

ci+1;k Fi;i+1 = 0.

This reasoning can run backward: if we have a transformation

P

between two sets of functions i = k di;k k whose coecients

di;k exhibit a three-term recurrence in k, the passage to the set

i corresponds to the diagonalization of a certain operator whose

matrix calculated on the set k is tridiagonal.

53

The hermiticity requirement for the operators associated to physical observables implies that if the matrix F is real, it has to be

symmetric with respect to the principal diagonal. Therefore if we

have a non-symmetric three term recurrence

ci 1 Xi 1 + ci Yi + ci+1 Zi+1 = 0

(1.80)

operator. The procedure that we adopt (e.g. in Sec. 4) is the

following. Let us demand ci = Qi gi , where the gi are the elements

that will enjoy the symmetric three term recurrence relationship.

Substitution in Eq. (1.80) and division by Qi lead to:

!

Q

Q

Xi 1 i 1 gi 1 + Yi gi + Zi+1 i+1 gi+1 = 0

Qi

Qi

(1.81)

Now let us impose the symmetry with respect to the principal diagonal:

Q

Q

Xi 1 i 1 = Zi i

Qi

Qi 1

Consequently we get the ratio Qi 1 =Qi , which is enough to get an

p

p

explicit symmetrized recurrence: Xi 1 Zigi 1 +Yigi + Xi Zi+1 gi+1 =

0. By such a procedure the Qi are determined to within a constant

that can be xed imposing normalization and a convention for an

overall phase factor.

Bibliography

[1] J. Patera and J. Winternitz. J. Math. Phys., 14:1130, 1973.

54

[2] E.G. Kalnins, W. Miller, and P. Winternitz. S.I.A.M. J. Appl.

Math., 30:630, 1976.

[3] H. Shull and P.-O. Lowdin. J. Chem. Phys., 30:617, 1959.

[4] M. Rotenberg. Ann. Phys. (N.Y.), 19:262, 1962.

[5] M. Rotenberg. Adv. At. Mol. Phys., 6:233, 1970.

[6] J. Avery. Hyperspherical Harmonics, Applications in Quantum

Theory. Kluwer Academic, Dordrecht, The Netherlands, 1989.

[7] J. Avery. Hyperspherical Harmonics and Generalized Sturmians. Kluwer Academic Publishers, Dordrecht, The Netherlands, 2000.

[8] V. Aquilanti, S. Cavalli, C. Coletti, D. Di Domenico, and

G. Grossi. Int. Rev. Phys. Chem., 20(4):673, 2001.

[9] V. Aquilanti and J. Avery. Adv. Quantum Chemistry, 39:71,

2001.

[10] W. Miller Jr. Symmetry and Separation of Variables. AddisonWesley Publishing Company, Reading, Massachusetts, 1977.

[11] W. Miller Jr. Lie Theory and Special Functions. Academic

Press, New York and London, 1968.

[12] V. Aquilanti, S. Cavalli, and M.B. Sevryuk. J. Math. Phys.,

34:3351, 1993.

55

[13] V. Aquilanti, S. Cavalli, and M.B. Sevryuk. J. Math. Phys.,

35:556, 1994.

[14] M. Hamermesh. Group Theory and its Application to Physical

Problems. Dover Publications, Inc., New York, 1989.

[15] C.A.Coulson and A.Joseph. Proc. Phys. Soc. London, 90:887,

1967.

[16] V. Aquilanti, S. Cavalli, and C. Coletti. Chem. Phys., 214:1,

1997.

[17] Stella M. Sung and Dudley R. Herschbach. J. Chem. Phys.,

95:7437, 1991.

[18] R. N. Zare. Angular Momentum. Wiley & Sons, New York,

1988.

[19] M. Abramowitz and I.A. Stegun. Handbook of Mathematical

Function. Dover, New York, 1964.

[20] P. M. Morse and H. Feshbach. Methods of Theoretical Physics.

McGraw-Hill, New York, 1953.

[21] V. Aquilanti, S. Cavalli, C. Coletti, and G. Grossi. Chem.

Phys., 209:405, 1996.

[22] B. R. Judd. Angular Momentum Theory for Diatomic

Molecules. Academic Press, New York, 1975.

56

[23] L.D. Landau and E.M. Lifshitz. Quantum Mechanics. Nonrelativistic Theory. Addison-Wesley Publishing Co., Reading

Mass., 1958.

[24] M.E. Rose. Elementary Theory of Angular Momentum. Wiley,

New York, 1957.

[25] D.A. Varshalovich, A.N. Moskalev, and V.K. Khersonskii.

Quantum Theory of Angular Momentum. World Scientic,

Singapore, 1988.

[26] D. Park. Z. Phys., 36:155, 1960.

[27] T. Regge. Nuovo Cimento, 10:544, 1958.

[28] V. Aquilanti, L. Beneventi, G. Grossi, and F. Vecchiocattivi.

J. Chem. Phys., 89:751, 1988.

[29] V. Aquilanti and G. Grossi. J. Chem. Phys., 73:1165, 1980.

[30] V. Aquilanti, S. Cavalli, and G. Grossi. Z. Phys. D., 36:215,

1996.

[31] V. Aquilanti, S. Cavalli, and G. Grossi. Theor. Chim. Acta,

79:283, 1991.

[32] V. Aquilanti and S. Cavalli. Few-Body Systems. Suppl.6: 573,

1992.

[33] K. Schulten and R.G. Gordon. Comp. Phys. Comm., 11:269,

1976.

57

[34] K. Schulten and R.G. Gordon. J. Math. Phys., 16:1961, 1975.

[35] V. Aquilanti, S. Cavalli, and D. De Fazio. J. Phys. Chem.,

99:15694, 1995.

[36] A.R. Collar. Quart. Journ. Mech. and Applied Math., 15:265,

1962.

[37] C.A.Coulson and P.D.Robinson. Proc. Phys. Soc. London,

71:815, 1958.

[38] M. Aubert, N. Bessis, and G. Bessis. Phys. Rev. A, 10:51,

1974.

[39] M. Aubert, N. Bessis, and G. Bessis. Phys.Rev. A, 10:61, 1974.

[40] P.D. Robinson. Proc. Phys. Soc. London, 71:828, 1958.

[41] T. Levitina and E. J. Brandas. Int. J. Quantum Chem., 65:601,

1997.

[42] T. Levitina, E. J. Brandas, and B. Larsson. Int. J. Quantum

Chem., 85(4-5):392, 2001.

[43] I. V. Komarov, L. I. Ponomarev, and S. Yu. Slavyanov.

Spheroidal and Coulomb Spheroidal Functions. Nauka,

Moskow, 1976.

[44] I.S. Gradshteyn and I.M. Ryzhik. Table of Integrals, Series

and Products. Academic Press, New York, 1980.

58

[45] C.A. Coulson and A. Joseph. Int. J. Quantum Chem., 1:337,

1967.

[46] E. T. Whittaker and G. N. Watson. A Course of Modern

Analysis. Cambridge University Press, London, 1935.

[47] J. Patera and P. Winternitz. Journal of Chemical Physics,

65:2725, 1976.

[48] L. Pauling and E.B. Wilson Jr. Introduction to Quantum Mechanics. McGraw-Hill, New York and London, 1935.

[49] V. Aquilanti, S. Cavalli, and C. Coletti. Phys. Rev. Lett.,

80:3209, 1998.

Chapter 2

Hydrogenic Orbitals in Momentum

Space and Hyperspherical Harmonics.

Elliptic Sturmian Basis Sets.

Summary

Momentum space hydrogenic orbitals can be regarded as orthonormal and complete Sturmian basis sets, and can be explicitly given in terms of (hyper)-spherical harmonics on the fourdimensional hypersphere S 3 . Among the alternative coordinate systems which allow separation of variables, the usual ones involving

parametrizations of the sphere S 3 by circular functions correspond

to canonical subgroup reduction chains; we also investigate harmonic "elliptic" sets (as e.g. obtained by parametrizations in terms

of Jacobi elliptic functions). In this chapter we list the canonical

hydrogenic Sturmian sets and the orthogonal transformations connecting them. The latter enjoy very useful three-term recurrence

59

60

relationships which allow their ecient calculations even for large

strings. We also consider modications needed when the conservation of the symmetry of Sturmians with respect to parity. Finally

we discuss some properties of elliptic hydrogenic Sturmians and

their relations with canonical Sturmians. Since elliptic Sturmians

cannot be expressed in closed form, it is important to nd expansions in a suitable basis set and to calculate the transformation

coecients. We derive three-term recursion relationships fullled

by the coecients of the transformation between elliptic Sturmians

and canonical Sturmians. A concluding discussion on the connections between conguration space and momentum space hydrogenic

Sturmians completes this chapter.

2.1 Introduction

The investigation of the non-relativistic Schrodinger equation for

hydrogenic atoms in momentum space has great relevance not only

for the obvious importance of the physical problem, but also because it allows the construction of basis sets enjoying dierent symmetry properties useful in atomic and molecular structure calculations and for the description of atoms in elds.

Hydrogenic orbitals in momentum space, rst obtained by Podolski and Pauling [1] by direct Fourier transform, can indeed be identied, within a normalization factor, with hyperspherical harmonics of a 4-dimensional sphere, as shown by Fock [2] through his

61

famous stereographic projection. Modernly they can be referred

to as momentum space Sturmians [3{7], being the counterpart of

the so called "natural spin" [8] or conguration space Sturmian

orbitals [9, 10], which are nding increasing applications in atomic

and molecular quantum chemistry. For recent reviews, see Refs. [11]

and [12]. The reciprocity existing between conguration and momentum space has to be applied with care when trying to extend all

the symmetry properties which can be found in momentum space,

to the corresponding conguration space Sturmians. The symmetry

and completeness properties of these sets make them in fact adapt

to solve quantum mechanical problems where the hyperspherical

symmetry of the kinetic energy operator is broken by the interaction potential, but the corresponding perturbation matrix elements

can be worked out explicitly, as in the case of Coulomb interactions.

In this chapter, after explaining the connection between the

hydrogen atom and the four-dimensional hypersphere (section 2),

we review and update the classication of hydrogenic Sturmians

in momentum space given in ref. [13] (section 3), requesting the

conservation of parity (section 4). In addition elliptic Sturmians in

momentum space are introduced (section V), in which the modulus

of Jacobi elliptic functions can be seen as an additional `degree of

freedom', making them more
exible with respect to the canonical

Sturmians. As also stressed in the concluding Sec. 6, the aim of

this chapter has been to show that they are less `intractable' than

previously believed [14].

62

2.2 Background

In 1935 Fock obtained the wavefunctions of hydrogen atom (p)

in momentum space, by solving the Schrodinger Equation related

by Fourier transform to the one in conguration space:

1 Z

(p2 + p20 ) (p) = 2

(p0 )

jp p0j2 dp

(2.1)

be used throughout this chapter). The wavefunctions (p) can be

related to 4-dimensional spherical harmonics, i.e. eigenfunctions

of the Laplace operator on S 3 . The momentum p with Cartesian

coordinates:

px = p sin # cos '

(2.2)

pz = p cos #

where p is the modulus of p and # and ' its polar angles, is projected onto a 4-dimensional hypersphere of unit radius:

2p p

x = 2 0 x2 = sin sin # cos '

p0 + p

2p p

y = 2 0 y2 = sin sin # sin '

p0 + p

2p p

z = 2 0 z2 = sin cos #

p0 + p

p2 p2

w = 02 2 = cos

p0 + p

(2.3)

63

where 0 . Eq. 2.3 exhibits the relationship between the

Euclidean space (px ; py ; pz ) and the S 3 surface (x2 + y 2 + z 2 + w2 =

1), and also gives an explicit parametrization in polar coordinates

(; #; ') of the S 3 hypersphere. Fig. 1 illustrates Fock's stereographic projection, but in order to make it readable we have drawn

it considering one dimension lower, i.e. projecting a 2-dimensional

plane on the 3-dimensional sphere S 2 , instead of the 3-dimensional

space on the 4-dimensional hypersphere S 3 .

The eigenfunction for the hydrogen atom in momentum space

is [6, 7, 12]:

n;l;m (p) =

4p50=2

Y (; #; ')

(p20 + p2 )2 n;l;m

(2.4)

the wave function for the free motion of a particle on the S 3 surface. Thus the principal quantum number n (which labels the energy spectrum) can appropriately be interpreted as a hyperangular

momentum quantum number, manifesting that the hidden symmetry giving rise to the accidental degeneracy emerging in the threedimensional conguration space treatment is actually a four dimensional symmetry, which has been analyzed and discussed in various

papers [15], reviews [16] and books [17]. The invariance group for

the hamiltonian of the hydrogen atom is thus O(4), the continuous

group of rotations in the four-dimensional Euclidean space. The

actual symmetry of the hydrogen atom Schrodinger equation has

therefore become apparent only in the momentum space approach:

64

u2

,

u1

u3

p1

p2

Figure 2.1:

points on a sphere S d 1 and a Euclidean space Rd . The case d = 3 is the

one used by Fock for the hydrogen atom (see Section 2). The familiar "geographic" case d = 2 is sho wn here for illustration: stereographic projection of

a point p in a plane with coordinates p1 = p sin ' and p2 = p cos ' onto the

surface of a sphere having unitary radius with coordinates u1 = sin # sin '; u2 =

sin # cos '; u3 = cos #, where cos # = (p20 p2 )=(p20 + p2 ). The shaded zone represents the projection of the points of the plane onto the part of spherical bowl

comprised between the equator and the axes u1 and u2 . The points fullling

the condition p = p0 are projected onto the equator.

65

the degeneracy existing for a given n gives rise to n2 Sturmians

which belong to the same irreducible representation of O(4).

The hydrogenic hamiltonian can be expressed as a function of

^

the orbital angular momentum ^l and of the Runge-Lenz vector A

^ [15, 18]:

in its reduced form K

1

^ 2 + 1) 1

H^ = (^l2 + K

2

where

(2.5)

1 ^

^l + np0r =p0

l

p

^

p

^

(2.6)

2

r

^ can be identied with the

The Cartesian components of ^l and K

generators of four-dimensional rotations, in virtue of the isomorphism of the hydrogen atom with the sphere S 3 . Let us consider

the Euclidean four-dimensional space: there are six possible distinct

bidimensional planes identied by the various couples of Cartesian

axes; by indicating one of those planes as ef , a rotation of an angle

upon it is performed by the operator eiJ^ef , where J^ef is one of

the six generators of O(4) [17, 19]:

K^ = A^ =p0 =

@

1

J^ef = ue

i

@uf

@

uf

@ue

(2.7)

fg J^eh

eh J^fg + eg J^fh

(2.8)

^ , on the basis of their commutation relations

components of ^l and K

66

[19]:

(2.9)

K^ x = J^14 K^ y = J^24 K^ z = J^34

The generalized Beltrami-Laplace operator for the motion in d dimensions can be written as [19]:

X

@2

1 @ d 1@

= d 1

r

2

@ue r @r

@r

1 X ^2

J

r2 f>e ef

(2.10)

A d-dimensional hyperspherical harmonic solves the eigenvalue equation on the d-dimensional sphere S d 1 parametrized by the set of

angles

d 1 :

X

b>a

J^ab2 Yj;(

d 1 ) = j (j + d 2) Yj;(

d 1 )

(2.11)

d = 4 one has a six-term sum:

X

b>a

J^ab2 Yj;(

3 ) = j (j + 2) Yj;(

3 )

(2.12)

where denotes two quantum numbers. Use of eq. (2.9) shows that

^ 2, and therefore

the operator in eq. (2.12) coincides with ^l2 + K

momentum space Sturmians (which, as we have seen, essentially

coincide with four-dimensional harmonics) can be identied with

basis sets for irreducible representations of the rotational group

O(4), as suggested by eq. (2.4). The hyperangular momentum

quantum number j = n 1 labels the energy levels.

That of eq. (2.3) is only one of the possible parametrizations

separating the Hamiltonian for the motion on S 3 (for it, = l; m):

67

starting from other suitable parametrizations alternative momentum space orbitals can be worked out. A complete classication of

the bases of O(4), including symmetry properties and connections

among them will be given in the following sections.

As mentioned in the previous section, the hyperspherical harmonics

in eq. (2.4) are not the only possible choice for four-dimensional

harmonics. Such a variety of choices is illustrated by the alternative ways of building the four-dimensional S 3 hypersphere starting

from lower dimension (hyper)-spheres. In particular there exist two

basically distinct ways which have been depicted in g. 2: the rst

one (g. 2a) consists of starting from the S 2 sphere (i.e. the physical three-dimensional sphere) and adding a rotation in the fourth

dimension. The "inverse" of this construction in group theory corresponds to the following chain reduction of O(4) into its subgroups:

O(4) O(3) O(2).

An alternative approach (g. 2b) starts from two S 1 circles,

each described by an angle, belonging to orthogonal R2 spaces and

then forms their product R2 R2 = R4 ; a third angle is needed

to cover S 3 . In group theory this corresponds to the subgroup reduction chain O(4) O(2) O(2). The related parametrizations

will be given the nicknames of asymmetric and symmetric for the

rst and second cases, respectively. Fig. 2 illustrates graphically

68

0

S (,,)

y = sin sin # sin '

z = sin cos #

w = cos

m

l

(a)

n-1

0 =2

3

S (,,)

y = sin sin '

z = cos sin

w = cos cos

z x

n-1

the asymmetric (a) and symmetric (b) parametrization. The relationship of

cartesian coordinates with spherical coordinates is obtained by labeling with

angular variables the intersections (nodes) between two tree "branches" and

considering that the branch converging to the node from the left (right) represents the cosine (sine) of the involved angle. Thus, starting from a leaf and

going down to the root of the tree, through the various nodes, we establish

a relation between cartesian coordinates and angles. Each of these angles is

related to rotations in a space whose dimension is equal to the number of the

upper free ends (or leaves), and thus to the corresponding rotation operator,

so that every node can also be labeled by its eigenvalue (quantum number).

Thus, in both types of parametrizations, according to the particular subspaces

involved in t he construction of S 3 we will have alternative basis sets of the

canonical type, i. e. corresponding to dierent subgroup reduction chains (see

also Ref. [43]).

Figure 2.2:

(b)

69

the two schemes for the construction of S 3 , and shows connections

between Cartesian and hyperspherical coordinates and the representation of the corresponding hyperspherical harmonics according

to the tree method. This graphical method, a full account of which

can be found in refs. [20{23], permits a visualization not only for the

connection between coordinates, but also for the rotation operators

for which the harmonics are eigenfunctions.

The following paragraphs will deal with the classication and

description of the various sets corresponding to the dierent parametrizations. Obviously the choice of a particular basis set is completely

pointless when the symmetry of the problem is the original S 3

one (as in the case of hydrogenoid atoms), but it becomes crucial when such a symmetry is broken, and yet the perturbation

hamiltonian can still be written in terms of the generators of the

four-dimensional rotation group, as in the case for instance for hydrogenoid atoms in electric and/or magnetic elds. Important in

quantum chemistry are molecular orbitals which describe symmetry

breakings occurring when atoms join to form molecules.

2.3.1

and Zeeman Sets

The harmonics in g. 2a correspond, as sketched before, to a subgroup reduction chain O(4) O(3) O(2), where a fourth dimension is added to the Euclidean tridimensional space [x; y; z ] whose

generators are ^lx , ^ly and ^lz , or according to the previous identi-

70

cation, J^12 , J^23 , J^13 (see Eq. 2.9). Explicitly these harmonics can

be written as the product between the usual tridimensional spherical harmonic Yl;m (#; '), eigenfunctions of the quadratic "orbital

angular momentum" operator ^l2 = ^lx2 + ^ly2 + ^lz2 with eigenvalues

l(l + 1), and a properly normalized Gegenbauer polynomial [24] of

the additional variable cos (Eq. 2.3):

(2.13)

"

#

2n(n 1 l)! 1=2

(2l + 2)

Bn;l = l+1

2 (l + 3=2)

(n + l + 1)

(2.14)

The harmonics Yn;l;m(; #; ') are also eigenfunctions of ^lz with eigenvalue m; this corresponds to the choice of the (xy ) plane where the

rotation subgroup O(2) acts and thus of z as the polar axis. Continuing to identify O(3) as acting on the tridimensional space [x; y; z ]

- the fourth dimension being not involved yet - when the (yz ) or

(xz ) planes are chosen for the O(2) subspaces one has the harmonics Yn;l;m0 (; #; '0 ) and Yn;l;m00 (; #; '00 ), eigenfunctions of ^ly (y

polar axis) and ^lx (x polar axis) respectively. Interchanges among

the polar axes, illustrated for example in g. 3, can be performed

by means of a Wigner rotation matrix:

m0

l

Dm;m

0 (0; =2; =2) Yn;l;m (; #; ')

(2.15)

Let us now consider a three-dimensional subspace where the rotation group O(3) acts, and let w be one of the axes: two of the

71

(a)

n-1

m

Wigner rotation matrix

n-1

Figure 2.3:

Representation of the change of quantization axis for the spherical basis sets from m (z axis) to m0 (y axis), corresponding to Eq. (2.15).

^ according to eq. (2.9). For example

components of the vector K

the basis [(xy )w]z described by tree (b) in g. 4 is diagonal with

respect to the operators K^ x2 + K^ y2 + ^lz2 and ^lz . Let the eigenvalue

corresponding to the rst operator be now denoted as ( + 1),

Labarthe's quantum number having the same range as l. This

basis set, which we call as a Zeeman basis, has been recently introduced [25{27]. It is useful for the treatment of the diamagnetism in

hydrogen atom and for the description of the behavior of Rydberg

atoms in magnetic elds. Note that, analogously to what has been

just shown for the spherical basis one can choose K^ y or K^ x as diagonal operators thus leading to Yn;;0 (0 ; 0 ; 0 ) and Yn;;00 (0 ; 00 ; 00 )

(b)

72

harmonics, where 0 and 00 denote the corresponding eigenvalues.

The connection between these bases and the Zeeman basis (compare

with the illustration in g. 3 of the case of the spherical basis) is

given by a Wigner rotation matrix, similar to eq. (2.15). Beside the

Zeeman basis set (and those basis sets with a dierent projection

axis, i.e. Yn;;0 (0 ; 0 ; 0) and Yn;;00 (0 ; 00 ; 00)), there are six other

bases of the same kind which can be identied: three of them are

eigenfunctions of the quadratic operator K^ x2 + ^ly2 + K^ z2 (with eigenvalue 0 (0 +1)) and of K^ x , ^ly and K^ z respectively (with eigenvalues

00 , m0 and ), while the last three bases are diagonalized by the

quadratic operator ^lx2 + K^ y2 + K^ z2 and by the operator ^lx , K^ y and

K^ z respectively (with eigenvalues m00 , 0 and ). A summary of the

twelve bases of O(4) corresponding to asymmetric parametrizations

in given in Table 1.

Orthogonal transformations which lead to a change in the tridimensional angular momentum quantum number (transformations

among l; ; 0 ; 00 ) can be performed by means of the Z matrices introduced in [13] (see also [28]). For example the orthogonal transformation between theP spherical (eq. 2.4) and the Zeeman basis

n;m

sets [Yn;l;m(; #; ') = Zl;

Yn;;m(0 ; ; ')] is depicted in g. 4.

In ref. [13] it was shown that the harmonic superposition between

the two bases, which had previously been dened indirectly through

the steps: Spherical basis ! Stark basis ! Zeeman basis and calculated as a sum on two vector coupling coecients [25,29] (see Eq.

2.22), can be written as a single sum of the Racah type:

n;m = ( )l+ [C (l)C ()]

Zl;

X

1

2

(2.16)

r!( l m2 p(l) r)!( m2 p() r)!( n+m+p(l2)+p()+1 + r)!(m + r)!

73

O(4) to the subgroup chain O(4) [O(3)]i;j;k [O(2)]i;j . The

bases are classied according to the diagonal operator acting on

the hyperplane [i; j; k] and to that acting on the plane (i; j ).

d = 3-subspace

d = 2-subspace

(x; y ) ^lz

(y; z ) ^lx

(z; x) ^ly

basis set

(x; y ) ^lz

(y; w) K^ y

(x; w) K^ x

jn; ; mi

jn; ; 0i

jn; ; 00i

(z; x) ^ly

(z; w) K^ z

(x; w) K^ x

jn; 0; m0 i

jn; 0; i

jn; 0; 00i

(y; z ) ^lx

(y; w) K^ z

(y; w) K^ y

jn; 00; i

jn; 00; 0i

jn; l; mi

jn; l; m00i

jn; l; m0i

74

(a)

/2

Z matrix

n-1

(b)

n-1

Figure 2.4:

which implies the change of the tridimensional quantum number from l to .

where

( n+2k 1 + p(k))!( k+2m q (k))!( k 2m q (k))! ( n 2 k + p(k))

C (k)= n+k+2

( 2 + p(k)) ( m+2k+1 + q (k)) ( k m2 +1 + q (k))( n 2k 1 p(k))!

n;m

is zero

p(k) = 1+( 41) and q (k) = ( 1) 4 1 . Note that Zl;

n;m

n; m

when n + l + + m is even and shows the symmetries Zl;

= Zl;

n;m

n;m

and Zl;

= Z;l

. The sum in 2.16 [28] is a hypergeometric function

4 F3 of unit argument and can be connected with Racah polynomials

[30, 31], although it cannot be reduced to the ordinary Racah's

or 6-j coecient which performs angular momentum recoupling.

Indeed, like a Racah's recoupling coecient it is orthogonal with

respect to summation on two angular momentum quantum numbers

(l and ), but contains a projection quantum number. As shown

n;m

in Ref. [13], the Z;l

coecient can be compactly written as a 6-j

symbol extended to allow not only multiples of 1/2, as ordinary

k n

k m

75

vector recoupling coecients, but also multiples of 1/4:

n;m = (

Zl;

l+

2

+1+p(l)+p() (l + 1 )( + 1 )

2

2

The symbol

1

4

1

4

p()

p(l)

n 1

2

m 1

2

l

1

4

1

4

(2.17)

so caution is needed in its use. Additional properties and relations

involving the Z matrix will be given in subsection 3.3.

2.3.2

Symmetric Parametrizations

We will deal now with the symmetric parametrizations, corresponding to the subgroup reduction chain O(4) O(2) O(2). The best

known of these basis sets is that corresponding through a Fourier

transform to the Sturmian orbitals written in parabolic coordinates

in conguration space (see chapter 1). Due to its importance in the

treatment of the hydrogen atom in an electric eld, we call the corresponding harmonic set as the Stark basis. For its use for building

molecular orbitals and multidimensional expansions, see [3,4,12,32].

This parametrization is illustrated in g. 2b and can be written as

z = cos sin w = cos cos

(2.18)

corresponding hyperspherical harmonics

4p50=2

n

n

1

m

n;;m (p) = 2 2 2 ( ) ({)

D (nm ;1) m ( '; 2; ' )

2

(p + p0 )

2

(2.19)

1

2

1

2

76

simultaneously diagonalize ^lz and K^ z (with eigenvalues m and ),

where we give to the z axis the role of a privileged direction in

physical space. This explains why the Hamiltonian for a hydrogen

atom in a weak electric eld directed along the z axis is still diagonal

in this basis. Similarly other two basis sets of this kind can be

constructed when the x and y axes are taken as quantization axes

(see Table 2). Thus we can have a basis diagonalizing ^lx and K^ x ,

and another one diagonalizing ^ly and K^ y , leading to a total of three

dierent basis sets corresponding to symmetric parametrizations.

The orthogonal transformation between spherical (g. 2a) and

Stark basis (g. 2b), analogously to what is found in conguration

space (see Chapter 1), is given by a Clebsch-Gordan coecient [33]:

cn;m

l; n;l;m (p)

(2.20)

1

m 1

m+

; (n 1);

jl; mi

cn;m

l; = h 2 (n 1);

2 2

2

(2.21)

n;;m (p) =

( )

1+m

2

we also have the connection between Zeeman and Stark basis sets.

Similarly to the treatment in conguration space, also in this case

it will be of importance to explicitly introduce parity conservation.

This will be done in Section 4.

2.3.3

O(4)

We have just shown that the number of distinct canonical basis sets

for S 3 amounts to 15. Actually the total number of solutions to

77

Laplace equation on S 3 (harmonics) is 120, however due to the fact

that for the identication of a plane or of a 3-dimensional space it is

only necessary to specify the involved axes and not their sequence,

to dierent systems of hyperspherical coordinates, identifying the

same plane, there correspond the same harmonics (or harmonics

diering for a phase factor only, i.e. still eigenfunctions of the

same rotation operator), so the number of dierent bases reduces

to 15. Ref. [13,34] provides a discussion on the classication of the

120 coordinate systems and of how this reduction is achieved. The

15 basis sets can be depicted together with their connections by

the graph in Fig. 5. This is a projective plane RP 2 representation,

which in turn can be obtained from a graph, associated to the

icosahedral group, illustrating the 120 coordinate systems (see ref.

[13]). The connections between dierent basis sets, which are placed

at the vertices of 10 triangles and 6 pentagons, are identied by

various types of segments: (i) vector coupling coecients (eq. 2.20)

are drawn by solid lines, (ii) rotation matrix elements (eq. 2.15) by

dotted lines and (iii) Z coecients (eq. 2.17) by zig-zag lines. Fig. 5

is also an "abacus" to obtain relationships among ordinary elements

of angular momentum algebra, augmented by the Z coecients:

following the sides of the plane gures one can write interesting

sum rules. For example following the side of the triangle where m

n;m

is conserved Zl;

can be written as a sum involving two ClebschGordan coecients

n;m =

Zl;

X

( ) h

(2.22)

n 1+m n 1 m

1+m n 1 m

;

;

; jl; 0ih

;

;

; j; 0i

2

2

2

2

2

2

2

2

(the phase = n 1 2m + l + is an integer: if it were omitted, the sum would be l ). We recognize on the right hand side

the transformation coecient used for the denition of the Zeeman

basis [25]. An alternative sum rule can be obtained from g. 5,

78

following the sides of a pentagon:

n;m X

0

dlm;m0 ( )Zl;

= ( 1)m+ dm;0 ( )

2

2

(2.23)

0

0

0

h n 12+ m ; 2 ; n 12

m0 0

n

; ; l; 0ih

1 + 0 m0 n 1 0 m0

;

;

; ; ; 0i

2

2

2

2

angular momentum theory [35], such as the Biedenharn and Elliott

identity (but also the Clebsch-Gordan series itself).

Other sum rules can be derived from g. 5 (some of them are

well known, as the addition formula for rotation matrices, obtained

following the sides of the triangle where l is conserved). Besides

those obtained by the graph in g. 5 the Z coecient enjoys other

interesting relations; here three-term recurrence relationships will

be given where only one of the quantum numbers is varied. Explicitly we have a three term recurrence relationship involving n:

n + 1q

[(n 1)2

l2 ][(n

1)2

2 ][(n

(l + 1)2 ]

1)2

n 2;m +

( + 1)2 ] Zl;

[(n 1)2

2 l + l + 2 l l2 + l2 + 2 l2 +

n;m

n2 (1 + + 2 + l + l2 2m2 n2 ) + 2m2 ] Zl;

+

n[

n

q

[(n + 1)2

1q

[(n + 1)2

l2 ][(n + 1)2

2 ]

(2.24)

n+2;m = 0

( + 1)2 ] Zl;

v

u

2

2l + 3 u

t (l

2

m2 )[(l

1)2

m2 ](n2 l2 )[n2

(2l 3)

(l

1)2 ]

Zln;m2;

79

000

111

000000000

111111111

000

111

000000000

111111111

000

111

00000000

11111111

00000000

11111111

000000000

111111111

000

111

11111111

00000000

00000000

11111111

000000000

111111111

00000000

11111111

000000000

111111111

00000000

11111111

000000000

111111111

00000000

11111111

000000

111111

000000000

111111111

00000000

11111111

000000000

111111111

00000000

11111111

000000

111111

000000000

111111111

00000000

11111111

00000000

11111111

000000

111111

000000000

111111111

00000000

11111111

00000000

11111111

000000

111111

000000000

111111111

00000000

11111111

00000000

11111111

000000

111111

000000000

111111111

00000000

11111111

000000000

111111111

000000

111111

000000000

111111111

00000000

11111111

000000000

111111111

000000

111111

000000000

111111111

00000

11111

00000000

11111111

000000000

111111111

000000

111111

000000000

111111111

0000011111111

11111

00000000

000000000

111111111

000000

111111

000000000

111111111

00000

11111

00000000

11111111

000000000

111111111

000000

111111

000000000

111111111

0000011111111

11111

00000000

000

111

000000000

111111111

000000

111111

000000000

111111111

0000011111111

11111

00000000

0000

1111

000

111

000000000

111111111

000000

111111

000

111

00000

11111

00000000

11111111

0000

1111

000

111

000000000

111111111

0000000

1111111

000

111

00000

11111

0000

1111

000

111

000000000

111111111

0000000

1111111

000

111

00000

11111

0000

1111

0000000001111

111111111

0000000

1111111

000

111

00000

11111

0000

000000000

111111111

0000000

1111111

000

111

00000

11111

0000

1111

000000000

111111111

0000000

1111111

000

00000

11111

0000111

1111

0000000001111

111111111

0000000

1111111

000

111

00000

11111

0000

000000000

111111111

0000000

1111111

000

111

00000

11111

0000

0000000001111

111111111

0000000

1111111

000

00000

11111

0000111

1111

0000000001111

111111111

0

1

0000000

1111111

000

111

00000

11111

0000

000000000

111111111

0

1

0000000

1111111

000

111

00000

11111

0000111

1111

000000000

111111111

0

1

0000000

1111111

000

00000

11111

0000

1111

0000000001111

111111111

0

1

0000000

1111111

000

111

00000

11111

0000

000000000

111111111

0

1

0000000

1111111

000

111

0000111

1111

000000

111111

000

111

000000000

111111111

0000000000

1111111111

000

000000000000

111111111111

0000

1111

000000

111111

000

111

00000000

11111111

0000000001111

111111111

0000000000

1111111111

000

111

000000000000

111111111111

0000

000000

111111

000

111

00000000

11111111

0000000000

1111111111

000

111

000000000000

111111111111

0000

1111

000000

111111

000

111

00000000

11111111

0000

1111

0000000000

1111111111

000

111

000000000000

111111111111

000000

111111

000

111

00000000

11111111

0000

1111

0000000000

1111111111

000000000000

111111111111

000000

111111

000

111

00000000

11111111

0000

1111

0000000000

1111111111

000000000000

111111111111

000000

111111

000

111

00000000

11111111

0000

1111

0000000000

1111111111

000000000000

111111111111

000000

111111

000

111

00000000

11111111

0000

1111

0000

1111

0000000000

1111111111

000000000000

111111111111

000000

111111

000

111

00000000

11111111

0000

1111

0000

1111

0000000000

1111111111

000000000000

111111111111

000000

111111

000

111

00000000

11111111

0000

1111

0000

1111

0000000000

1111111111

000000000000

111111111111

000000

111111

000

111

00000000

11111111

0000

1111

0000

1111

0000000000

1111111111

000000000000

111111111111

000000

111111

000

111

00000000

11111111

0000

1111

0000

1111

0000000000

1111111111

000000000000

111111111111

000000

111111

000

111

00000000

11111111

0000

1111

0000

1111

0000000000

1111111111

000000000000

111111111111

000000

111111

000

111

00000000

11111111

0000

1111

0000

1111

000000

111111

000000000000

111111111111

000000

111111

00000000

11111111

0000

1111

0000

1111

000000

111111

000000000000

111111111111

000000

111111

000000000

111111111

00000000

11111111

0000

1111

00000000

11111111

0000

1111

000000

111111

000000

111111

000000000

111111111

00000000

11111111

0000

1111

00000000

11111111

0000

1111

000000

111111

000000000

111111111

00000000

11111111

0000

1111

00000000

11111111

0000

1111

000000

111111

000000000

111111111

00000000111111111

11111111

0000

1111

00000000

11111111

0000

1111

000000

111111

000000000

00000000

11111111

0000

1111

00000000

11111111

0000

1111

000000

111111

000000000

111111111

00000000

11111111

00000000

11111111

000

111

000000

111111

000000000

111111111

00000000

11111111

00000000

11111111

000000000

111111111

000

111

000000

111111

000000000

111111111

00000000

11111111

00000000

11111111

000000000

111111111

000

111

000000

111111

000000000

111111111

00000000

11111111

00000000

11111111

000000000

111111111

000

111

000000

111111

000000000

111111111

00000000

11111111

000000000

111111111

000000

111111

000000000

111111111

00000000

11111111

000000000

111111111

000000

111111

000000000

111111111

00000000

11111111

000000000

111111111

000000

111111

000000000

111111111

00000000

11111111

000000000

111111111

000

111

000000

111111

000000000

111111111

00000000

11111111

000000000

111111111

000

111

00000000

11111111

000000000

111111111

000000000

111111111

000

111

00000000

11111111

000000000

111111111

000000000

111111111

00000000

11111111

000000000

111111111

00000000

11111111

| l m>

| >

| m>

| >

| l m>

|l m>

| m>

|m>

|m>

|> |

> |>

|>

|m>

| m>

Figure 2.5:

Each basis is labeled by two quantum numbers in the graph, while the quantum

number n has not been inserted explicitly, because it labels all the bases.

80

1

pn + 2

2l + 1

4l2 4l2 2 + 2m2 (l2 + l 1) + 2n2 (l2 + l 1 + 2m2 )] Zln;m2;

+

2l

1 [(l + 1)2

m2 ][(l + 2)2

m2 ][n2

2l + 5

(l + 1)2 ][n2

Zln;m

+2; = 0

(l + 2)2 ]

(2.25)

or m:

m + 1q

( m + 2)(l m + 2)[(m 1)2 2 ]

2

q

n;m 2

(l + m)( + m)(l + m)[(m 1)2 l2 ] Zl;

+ m[

2

l + l + l2

l2 + l2 + l2 2

n;m

+m2 (1 + + 2 + l + l2 m2 2n2 ) + 2n2 ] Zl;

m 1q

( m)(l m)[(m + 1)2 2 ]

(2.26)

2

q

[(m + 1)2 l2 ]( + m + 2)(l + m + 2) Zl;n;m+2 = 0

Note that these relations are extremely useful for calculation of full

strings of coecients.

Sturmians

An issue of great relevance is the conservation of the parity with

respect to the inversion of electronic coordinates in the transformations among O(4) bases: such a symmetry is present in many

81

physical systems and thus it is important to have Sturmian bases

with denite parity.

2.4.1

Sturmian orbitals in conguration space (see previous chapter).

Since the momentum space Sturmian in eq. (2.4) is the Fourier

transform of polar orbitals in the conguration space, it must have

the same symmetry properties: thus for the inversion one has

(2.27)

(px ; py ; pz ). As we did in the previous chapter for the parabolic

basis in conguration space, because of the complete reciprocity

between the two spaces, Stark Sturmians with the correct parity

n;jj;m (p) can be built by the formula ( = 1 is the parity with

respect to inversion)

n;jj;m(p) = jn; ; m; i =

p1

[ n;;m(p) ( )m n;

p)]

;m (

(2.28)

and the conservation of parity in the passage to the set n;l;m(p)

involves the parity-conserving Clebsch-Gordan coecients (pCG):

hn; l; m j n; ; m; i = (

1+m

2

Cl;n;m;

jj = ( )

1+m

2

1 + ( )l n;m

cl;jj

2(1 + ;0 )

(2.29)

82

which have been dened in the previous chapter Eq. (1.31), Sec.

1.3.

2.4.2

Zeeman sets. They do not correspond to any Sturmian orbitals in

conguration space. In order to study their behavior with respect to

the inversion, let us consider the tree in g. 4b; the corresponding

parametrization is:

2p p

x = 2 0 x2 = cos 0 sin cos '

p0 + p

2p p

(2.30)

y = 2 0 y2 = cos 0 sin sin '

p0 + p

2p p

z = 2 0 z2 = sin 0

p0 + p

p2 p2

w = 02 2 = cos 0 cos

p0 + p

As a consequence one has the following relationships among the

coordinates (px ; py ; pz ) in momentum space and the angles (0 ; ; ')

of the Zeeman parametrization of the 4-dimensional sphere S 3 on

which the 3-dimensional momentum space has been projected:

p2 + p2

px = 0

cos 0 sin cos '

2p0

p2 + p2

cos 0 sin sin '

(2.31)

py = 0

2p0

p2 + p2

pz = 0

sin 0

2p0

83

The corresponding momentum space Sturmian can be expressed as

(see eq. 2.13):

n;;m (p) =

4p5=2

( )n 1 jmj ({)+m jmj 2 0 2 2 Bn; cos 0 Cn+11 (sin 0 ) Y;m(; ')

(p0 + p )

(2.32)

where Bn; had been dened in eq. (2.14). Taking into account

that inversion changes the sign of p = (px; py ; pz ) but leaves p2

unchanged, from eqs. (2.30) and (2.31) one sees that such an operation corresponds to the transformation of angles (0 ; ; ') into

( 0 ; ; ' + ). Considering that

and that

one has:

1 C +1 (sin 0 )

n 1

eim('+) = ( )m eim'

P^ n;;m (p) = ( )n

1+m

n;;m(p)

(2.33)

Thus we have shown that the basis n;;m (p) is the set of eigenfunctions of the operator which performs the inversion of p, and the

same proof applies to the bases n;0 ;m0 (p) and n;00 ;m00 (p), thus

the three matrices Z which - as in g. 4 - perform the transformation to the functions n;l;m(p), n;l;m0 (p) and n;l;m00 (p) should

be factorized in two blocks, in order to conserve the parity. These

conclusions are consistent with the observation that the matrix eln;m

ements Zl;

are zero when n + l + + m is even [13, 36].

84

The transformation between Stark and Zeeman basis sets (eq.

2.20 with instead of l) involves the pCG coecients, which have

been amended by requesting the conservation of parity [compare

with eq. (2.29)]. One has to consider that the Zeeman basis set has

parity ( )n 1+m :

p)

n;jj;m(

n X

jmj 1

( )

jj=0 or 1

C;n;m;

jj =

1+m

2

C;n;m;

jj n;;m (p)

c;

2(1 + ;0 )

(2.34)

matrices. In Fig. 5 there are four triangles whose three sides are

represented by dotted segments. In one of these, l remains a good

quantum number and so does parity, which is ( 1)l for spherical

bases. For the other three triangles, the situation diers because of

those vertices which correspond to Zeeman Sturmians that diago^ . Since K^ and P^ do not

nalize one of the Cartesian components of K

commute, those functions cannot be simultaneously eigenfunctions

of P^ . For deniteness, let us consider the Sturmian n;;00 (p); the

corresponding parametrization is:

2p p

x = 2 0 x2 = cos 0 sin 0 cos '00

p0 + p

2p p

y = 2 0 y2 = cos 0 cos 0

p0 + p

2p p

z = 2 0 z2 = sin 0

p0 + p

(2.35)

85

p2 p2

w = 02 2 = cos 0 sin 0 sin '00

p0 + p

thus one can write

p2 + p2

cos 0 sin cos '00

px = 0

2p0

p2 + p2

py = 0

cos 0 cos

(2.36)

2p0

p2 + p2

sin 0

pz = 0

2p0

Therefore the inversion of p in the tridimensional space corresponds

to the transformation of angles (0 ; ; '00 ) ! ( 0 ; ; '00 ).

The expression of the Sturmian is, apart from a normalization factor

which is not needed for symmetry considerations:

p50=2

0 C +1 (sin 0 ) P j00 j (cos ) ei00 '00

cos

n 1

2

(p0 + p2 )2

(2.37)

Because of the change in the sign of the argument of the exponential

function as a consequence of the inversion, it is evident that the

Sturmian in eq. (2.37) cannot be eigenfunction of P^ . Applying

the projection procedure (p) = p12 [ n;;00 (p) n;;00 ( p)] one

can work out:

n;;00 (p) =

n;;j00 j (p) =

p1

n;;00 (p) ( )n

00 1

p)

n;; 00 (

(2.38)

is completely analogous to the one we had in the construction of

denite parity Stark Sturmians (eq. 2.28): in order to obtain the

86

parity components of a Sturmian which was originally eigenfunction

for one of the K's Cartesian components, one has to combine two

Sturmians having opposite values of (or 0 or 00 ). Thus, the

orthogonal transformation

n;;m (p) =

00

Dm;

00

n;;00 (p)

n;;m(p) =

00

;

Dm;

j00 j (0; =2; =2) n;;00 (p)

where

;

Dm;

j00 j (0; =2; =2) =

1+

( )n 1+m

q

Dm;00 (0; =2; =2) (2.39)

2(1 + 00 ;0 )

The form of eq. (2.39) is due to the fact that matrix elements

00 (0; =2; =2) diering only in the sign of 00 can only have

Dm;

equal or opposite values.

In summary, the basis sets which have (or 0 or 00 ) as a

quantum number can be turned into "parity Sturmians" performing

a linear combination with the Sturmians labeled by (or 0 or

00 ). These "parity Sturmians" will no longer be labeled by

(or 0 or 00 ), but by jj (or j0 j or j00 j) plus , the eigenvalue

of the inversion operator P^ . As a consequence, matrix elements of

orthogonal transformations where jj (or j0j or j00 j) is conserved as

a quantum number have to be premultiplied by the suitable parity

factor, which appears in eqs. (2.29),(2.34) and (2.39).

87

Besides the canonical (i.e. canonical) bases described in previous

sections - deriving from parametrizations of the hypersphere S 3 in

terms of the well known circular function sin and cos - there exist, as is described in Refs. [15, 37], bases of O(4) resulting from

elliptic parametrizations of S 3 . Such parametrizations can be set

up by Jacobi elliptic functions sn(a; k), cn(a; k) and dn(a; k) [24],

and represented by ternary forks (see Fig. 6) [38]. Trigonometric

alternatives are also useful, but a crucial fact is that the value one

gets for such functions depends also on a number, k, called modulus,

that can have any value in the range [0; 1]. Thus, it is understood

that the Sturmians coming from elliptic parametrizations will have

an additional "degree of freedom" (the modulus) with respect to

the canonical Sturmians: the former are more " exible", but their

manipulation is more complicated - for example they can not be

expressed in a closed form - and in fact, as far as we know, they

have never been used for the calculation of properties of atomic and

molecular systems other than the hydrogen atom. In the following,

we will analyze the symmetry properties of elliptic sturmians, in order to clarify their relation with canonical Sturmians and to insert

them in the overall scheme of the alternative hydrogenic Sturmians. Since elliptic Sturmians cannot be expressed in closed form,

one has to expand them in some suitable basis set and calculate

the coecients of the expansion: the three-term recursion relation-

88

ships fullled by the transformation coecients among canonical

and elliptic Sturmians will be given.

2.5.1

parametrization of the hypersphere S 3 in spheroelliptic coordinates

(see g.6a):

w = cos

(2.40)

The constants of motion for the corresponding harmonics are ^l2 +

K^ 2, ^l2 and ^lx2 + k02^ly2 [15, 37]. The momentum space Sturmian set

resulting from the parametrization (2.40) is the Fourier transform of

the corresponding counterpart in conguration space, introduced in

ref. [37] and analyzed in Chapter 1, as it can be seen by comparing

operators and coordinates of the two reciprocal spaces.

We will now deal with elliptic parametrizations, deriving from

elliptic cylindrical coordinates of type I and II, which don't have

a counterpart in conguration space (the answer to the intriguing

question of why some elliptic Sturmians in momentum space do not

have counterparts in conguration space will be given in Section 6).

89

l, (k)

(a)

n-1

(b)

n-1, b(k)

m

,

(c)

n-1, q(k)

[spheroelliptic (a), elliptic cylindrical of type I (b), elliptic cylindrical of type II

(c)]. Although several alternatives are possible, we found it useful [38], exploiting results from Ref. [37] for S 2 and Ref. [15] for S 3 , to adopt the following

conventions: in the denitions of coordinates, a left branch corresponds to

sn(; k )dn(; k 0 ), a middle branch corresponds to cn(; k )cn(; k 0 ), and a right

branch corresponds to dn(; k )sn(; k 0 ). The arguments and of the elliptic

functions are the variables; the modulus parameter k [and k 0 = (1 k 2 )1=2 ,

with 0 k; k 0 1] adds a degree of freedom to these coordinate systems.

The labels b; q; are separation constants depending on k and in general are

to be determined as eigenvalues of secular equations. For S 3 , the most general separable coordinates (the ellipsoidal [15]) would accordingly be put into

correspondence with "quaternary" forks (they depend essentially on two independent parameters which span the projective plane of Fig. 5). The procedure

can be extended to S d 1 for which trees involving forks of up to the d-th order can be dened (using results from Ref. [44], where dierent but equivalent

graphs were introduced).

Figure 2.6:

90

2.5.2

and II

6b):

z = sn(; k) dn(; k0)

w = cn(; k) cn(; k0 )

(2.41)

(

cos m'

The corresponding hyper-harmonics are given as L()L0( )

sin m'

0

where L() and L ( ) are solutions of equations related to the socalled associated Lame equation [15]: these solutions are not available in closed form, but information on a certain basis set and on

its connections with the others can be obtained by studying the

corresponding commuting operators.

By setting F^j = 2i (^lj + K^ j ) and G^ j = 2i (^lj K^ j ) (j = x; y; z )

such operators are [15]:

^ 2 + G^ 2)

C^ = 2(F

(2.42)

!

k2 + 1 ^ ^

^

^

^

^

^

B = Fx Gx + Fy Gy + 2

FG

k 1 z z

R^ = (F^z + G^ z )2

(2.43)

(2.44)

we will obtain equivalent commuting operators which can be more

^ 2 = G^ 2 =

readily interpreted. Considering that l K = 0, one has F

1 ^2 ^ 2

^ 2

^2

^

4 (l + K ). From eq. (2.44) it follows R = ( {lz ) = lz . So,

91

the meaning of C^ and R^ is clear: they are absolutely equivalent to

^ 2 and ^lz2. Now we have to explain the

the familiar operators ^l2 + K

meaning of the operator B^ . Eq. (2.43) can be rewritten as

F^ G^ =

k2 1 z z

1 (^lz + K^ z )(^lz K^ z )

^ G^

=F

k2 1

2

^

^

The product F G can be expressed as:

^2 ^

F^ G^ = 12 (F^ + G^ )2 12 (F^ 2 + G^ 2) = l2 + C4

Therefore the elliptic cylindrical harmonics of type I diagonalize

the operator

^l2 C^ 1 (^lz + K^ z )(^lz K^ z )

+

2 4

k2 1

2

Multiplying by -2 and expanding, the latter is found to be equivalent to

^l2 + 1 2 K^ z2 + 2 1 ^lz2 C^

(2.45)

1 k

k 1

2

Consequently, the basis can be characterized by the set of operators

^l2 + K^ 2, ^l2 + 1 1k K^ z2 and ^lz2. In the limit k ! 0, the second one

tends to ^lx2 +^ly2 +^lz2 + K^ z2 , which by an appropriate linear combination

with C^ and ^lz2 gives K^ x2 + K^ y2 + ^lz2 : this is tantamount to say that

the elliptic cylindrical harmonics of type I tend, in this limit, to

the Zeeman set Yn;;m . In the opposite limit, the operator tends to

K^ z2 , thus the set tends to that of denite parity Stark harmonics

Yn; jj;m.

2

92

The elliptic cylindrical coordinates of type II are (see g. 6c):

z = sn(; k) dn(; k0 );

The operators which characterize the corresponding set of hyperharmonics are the ones in eqs. (2.42) and (2.44), plus [15]

(2.48)

By some passages similar to the ones we made for the elliptic base

of type I, Q^ can be written as:

^l2 k2 ^ ^ ^ ^ C^

+ (l + Kz )(lz Kz ) +

Q^ =

2 2 z

4

A more perspective equivalent expression for this operator is

^l2 + k2K^ z2 k2^lz2 C^

(2.49)

2

Therefore this basis can be characterized by the set of operators

^l2 + K^ 2, ^l2 + k2K^ z2 and ^lz2. As k ! 0 it goes into the spherical basis,

since ^l2 + k2 K^ z2 ! ^l2 , while as k ! 1 one has the operator ^l2 + K^ z2 ,

which by linear combination with C^ and R^ is seen to correspond to

the operator which characterizes the Zeeman basis.

Now we can insert the elliptic cylindrical bases of type I and

II in a scheme (gure 7) where their relationships with the other

bases are shown. The basis I, as the modulus k varies, changes

continuously from Yn;;m to Yn; jj;m, and the basis II from Yn;l;m to

Yn;;m .

93

y w

n1, q(k)

n1, b(k)

Ell. Cylindrical

type II

k

1

lm

nm

Z l

z

Ell. Cylindrical

type I

k

k

C ||

m

n1

n1

z

n1

Figure 2.7:

n1

|| m

nm

Relationships among elliptic and canonical Sturmians. For limiting values of the modulus k , the elliptic Sturmians coincide with the canonical

ones, i.e. those corresponding to binary trees.

94

It is possible to get the unknown elliptic cylindrical eigenfunctions by calculating the coecients of their expansion in suitable

basis sets. As we diagonalize the matrix of ^l2 + k2 K^ z2 on the basis

^ 2 and ^lz2, therefore

Yn;l;m, the eigenvectors diagonalize also ^l2 + K

they are elliptic cylindrical functions of type II. By calculating the

matrix of the operator ^l2 + k2 K^ z2 on the basis Yn;l;m we can prove

P

that the coecients in Yn;q;m

= l bn;m;

q;l Yn;l;m - where Yn;q;m is the

elliptic cylindrical basis set of type II and q is the eigenvalue of

^l2 + k2K^ z2 - are related by the three-term recursion relationship

r

k2 [n (l 1)(2][(l l3)(2

q;l 2

l 1) (2l+1)

(l+1) m ][n (l+1) ]

l m ][n l ]

l(l + 1) + k2 [ (2l+1)(2

+ k2 [ (2l 1)(2

l+3)

l+1)

2

k2 [n (l+2) ][(l+2)

(2l+1)(2l+3) (2l+5)

2

q bn;m;

q;l +

m ] n;m;

bq;l+2

2

=0

(2.50)

be any number) thus matrix elements hYn;l;mj^l2 + aK^ z2 jYn;l0;m i are

always zero if l and l0 have dierent parity, and elliptic cylindrical

functions have denite inversion symmetry , indicated by = 1.

As k ! 0, eq. (2.50) is diagonal, while as k ! 1 it becomes a

n;m

recursion in l for the coecients Zl;

(see Eq. 2.24) where the

eigenvalue q corresponds to (n2 1) ( + 1) + m2 , since the

operator tends to ^l2 + K^ z2 which can be written as 4C^ (K^ x2 +

K^ y2 + ^lz2 ) + ^lz2 .

As another example of application of this method, let us calh

95

culate the overlaps, i.e. the transformation coecients, between

Yn;b;m

(the elliptic cylindrical basis set of type I, where b is the

eigenvalue of the operator ^l2 + 1 1k K^ z ) and Yn; jj;m. Putting

P

Yn;b;m = jj an;m;

b;jj Yn;jj;m one has, by calculating the matrix of

^l2 + 1 1k K^ z2 on the basis Yn; jj;m:

2

1 2

[n (m + 1)2 ] [n2 (m + 1)2 ] an;m;

b;j 2j +

4

1 2

1

1

(n 1) + (m2 2 ) +

2 b an;m;

b;jj +

2

2

2

1 k

1q 2

[n (m + + 1)2 ] [n2 (m 1)2 ] an;m;

b;j+2j = 0 (2.51)

4

According to the scheme of gure 7, the latter recurrence relationship is diagonal as k ! 1, while as k ! 0 eq. (2.51), it coincides

with the recursion in for the coecients C;n;m;

jj , and the eigenvalue b becomes (n2 1) ( + 1) + m2 . In g. 8 we show the

correlation diagrams for the separation constants b and q of the elliptic cylindrical orbitals of type I and II in the case n = 3; m = 0.

q

The scope of this chapter has been to oer a complete view of

hydrogenic orbitals in momentum space, which essentially coincide

with harmonics on the hypersphere S 3 . From the alternative sets of

coordinates for which the Laplace equation on the hypersphere separates, dierent sets of orbitals originate: we have classied them

and studied some of their properties, particularly investigating the

96

4

Elliptic Cylindrical Basis, Type II

q

n+k

0

2

Arctan k

Figure 2.8:

/4

b

2

n+1/(1-k )

0

/2

Arctan 1/(1-k )

numbers b and q as a function of k 2 , for the case n = 3; m = 0. Left panel:

case of elliptic cylindrical basis set of type II. Right panel: case of elliptic

cylindrical basis set of type I. On the left extreme, q coincides with l(l + 1); at

the opposite side, b coincides with 2 . In the middle of the diagram, both of

them coincide with (n2 1) ( 1) + m2 (Zeeman basis set).

97

connections between them. Within the framework of information

already available in the literature [4, 13] we have introduced explicitly the requirement of the conservation of parity with respect

to inversion and have obtained three-term recurrence relationships

for the transformation coecients, including the Z -matrix elements

recently dened [25, 26, 39]. Our detailed investigation has lead to

three-term recurrence relationships which provide a simple calculation scheme for the development of cylindrical elliptic orbitals of

rst and second type both in the familiar spherical and in the Stark

orbitals. This also has allowed to elucidate the relationships with

respect to the `canonical' bases.

Finally, amplifying the results of the previous chapter which

focused on orbitals in conguration space, we can discuss analogies and dierences of the obtained basis sets in the two reciprocal

spaces. Of the four types of orbitals in conguration space, three

of them (polar, parabolic, spheroelliptic) have a counterpart in momentum space (spherical, Stark, spheroelliptic) respectively. The

fourth type of orbitals (spheroidal), characterized by being eigenfunction of the operator ^l2 + 2K^ z , has no counterpart in momentum space. On the other hand, three types of orbitals among those

available in momentum space (Zeeman, elliptic cylindrical of type

I, elliptic cylindrical of type II) characterized respectively by being

eigenfunctions of the operators K^ x2 + K^ y2 + ^lz2 , ^l2 + 1=(1 k2 )K^ z2

and ^l2 + k2 K^ z2 , have no counterpart in conguration space. The

reason for this "missing correspondence" (one manifestation being

98

the intractability of spheroidal orbitals according to Coulson [14])

^ operator: according

can be attributed to the dierent role of the K

to its denition (Eq. 2.6), it can be seen that it is a second order

dierential operator in conguration space, while it acts as a rst

order dierential operator on eigenfunctions in momentum space.

This is at variance with the role of ^l, which is of the rst order in

both spaces. Since the conguration space Schrodinger equation

is of the second order, as it is its counterpart describing motion

on S 3 , separability of variables implies the action of second order

operators [15, 40]. On the other hand in conguration space there

^ 2 (or any of its cartesian

are no diagonal operators which contain K

components).

The fact that each alternative type of orbitals in momentum

space provides eigenfunctions of cartesian components of ^l2 and

K^ 2 or of their linear combinations, also implies that these orbital

sets induce irreducible representations in the group D2h [15]: the

correspondence holds for the reciprocal conguration space only

in the case of polar, parabolic and spheroelliptic orbitals, which

also induce irreducible representations in D2h , while the spheroidal

orbitals do not.

A detailed description of Sturmian basis sets and of their counterpart in momentum space is extremely important for the implementation of the remarkable plane wave expansion:

exp(ip r) = (2 )3=2

p2 + p2

un;l;m(r) 0 2 n;l;m (p)

2p0

n;l;m

X

(2.52)

99

which is seen to be essentially an expansion in four-dimensional

spherical harmonics and Sturmian polar orbitals (their explicit expression can be found in the previous chapter. Eq. (2.52) is a key

formula in momentum space quantum chemistry and was introduced by Shibuya and Wulfman [41] in 1965 who used it to expand

one-electron molecular orbitals and to obtain secular equations for

multicenter problems. A detailed mathematical analysis for such

an expansion can be found in ref. [42].

Previously, we had introduced an extension of such a formulation to Stark Sturmians [3], which has proved to have competitive convergence properties when applied to the calculation of the

ground state energy of the hydrogen molecular ion. This research

has emphasized the importance of exploiting the diverse alternative

separable coordinate systems. The extension of such expansions to

the dierent types orbitals treated in this chapter seems extremely

promising and stimulating, not only in the three-dimensional case,

but also in the d-dimensional wave expansion, as already done [4]

for spherical and Stark Sturmians. The solution of many-body

Coulomb problems would in fact require multidimensional plane

wave expansions [12].

Bibliography

[1] B. Podolsky and L. Pauling.

[2] V. Fock.

100

[3] V. Aquilanti, S. Cavalli, C. Coletti, and G. Grossi.

Phys., 209:405, 1996.

[4] V. Aquilanti, S. Cavalli, and C. Coletti.

1997.

Chem.

[6] J. Avery. Hyperspherical Harmonics, Applications in Quantum

Theory. Kluwer Academic, Dordrecht, The Netherlands, 1989.

[7] J. Avery. Hyperspherical Harmonics and Generalized Sturmians. Kluwer Academic Publishers, Dordrecht, The Netherlands, 2000.

[8] H. Shull and P.-O. Lowdin.

[9] M. Rotenberg.

[10] M. Rotenberg.

2001.

G. Grossi. Int. Rev. Phys. Chem., 20(4):673, 2001.

[13] V. Aquilanti, S. Cavalli, and C. Coletti.

80:3209, 1998.

101

[14] C.A.Coulson and A.Joseph.

1967.

Math., 30:630, 1976.

[16] M. Bander and C. Itzykson.

Wiley-Interscience, New York, 1972.

[18] L.D. Landau and E.M. Lifshitz. Quantum Mechanics. Nonrelativistic Theory. Addison-Wesley Publishing Co., Reading

Mass., 1958.

[19] B. R. Judd. Angular Momentum Theory

Molecules. Academic Press, New York, 1975.

[20] Yu.F. Smirnov and K.V. Shitikova.

1976.

for Diatomic

Representation des Groupes. Dunod, Paris, 1969.

J. Nucl. Phys., 2:645, 1966.

[23] V. Aquilanti, S. Cavalli, C. Coletti, D. De Fazio, and G. Grossi.

In C.A. Tsipis, V.S. Popov, D.R. Herschbach, and J.S. Avery,

102

editors, New Methods in

1996.

Function. Dover, New York, 1964.

[25] J.J. Labarthe.

of Mathematical

et Marie Curie, Paris, 1988.

[28] C. Coletti.

1988.

[30] A.F. Nikiforov, S.K. Suslov, and V.B. Uvarov. Classical Orthogonal Polynomials of a Discrete Variable. Springer-Verlag,

Berlin, 1991.

[31] V. Aquilanti, S. Cavalli, and C. Coletti.

344:587, 2001.

G. Grossi. Quantum Systems in Chemistry and Physics. Vol

I: Basic Problems and Model Systems, page 289, 2000.

[33] D. Park.

103

[34] V. Aquilanti and C. Coletti. Chem. Phys. Lett., 344:601, 2001.

[35] V. Aquilanti, S. Cavalli, and G. Grossi.

1996.

[37] J. Patera and J. Winternitz. J. Math. Phys., 14:1130, 1973.

[38] V. Aquilanti, S. Cavalli, and G. Grossi. J. Chem. Phys.,

[36] M. Kil'dyushov.

85:1362, 1986.

[40] W. Miller Jr. Symmetry and Separation of Variables. Addison[39] D. Delande and J.C. Gay.

1965.

[42] E. J. Weniger.

[43] A. A. Izmest'ev, G. S. Pogosyan, A. N. Sissakian, and P. Winternitz. J. Math. Phys., 40:1549, 1999.

[44] E. G. Kalnins and Jr. W. Miller.

1986.

104

O(4) to the subgroup chain O(4) [O(2)]i;j [O(2)]k;l. The bases

are classied according to the diagonal operator acting on the planes

(i; j ) and (k; l).

d = 2-subspace d = 2-subspace

(y; z ) ^lx

(x; w) K^ x

basis set

jn; 00; mi

(z; x) ^ly

(y; w) K^ y

jn; 0; mi

(x; y ) ^lz

(z; w) K^ z

jn; ; mi

Chapter 3

Many-electron one-center systems

Summary

This chapter deals with the application of polar Sturmian orbitals to the solution of the Schrodinger equation for free atoms

and atoms in external elds. We dene a N -electronic generalized

Sturmian basis set as a product of one-electron Sturmian orbitals.

Expanding the electronic wavefunction by such a generalized Sturmian basis set, we obtain a secular problem in which the matrix

elements do not contain any kinetic energy operator. The solution of the secular problem yields accurate values for the energies

of electronic ground and excited states. In the Sturmian method

framework, the eect of strong external elds can be taken into

account with little additional eort; we provide the formalism for

the treatment of external perturbation and show the results of a

preliminary calculation for static polarizability of Lithium.

105

106

3.1 Introduction

Chapters 1 and 2 contain a deep insight into the properties of the

dierent species of hydrogenic Sturmian orbitals. In this chapter

we will see the application of polar Sturmian orbitals (Eq. 1.7),

to the calculations of physical properties for isolated atoms. Illustrating the approach to atomic structure as a many-electron

one-nucleus problem, we discuss here the procedure of building a

polyelectronic basis set as a product of "monoelectronic" Sturmian

orbitals [1{3, 7, 9, 11, 12]: an alternative method, which denes N electronic Sturmians as solutions of the 3N -dimensional hydrogen

atom can be elegantly formulated and also has a momentum space

counterpart in terms of hyperspherical harmonics [4{6], but still

lacks of developments in the algebraic and computational implementation in order to be computationally competitive.

Sturmian approach is quite dierent from the procedure used

commonly in modern ab initio quantum chemistry:

The one-electron orbitals are Sturmian orbitals. Their analytic expression is known a priori, except the exponent of

the radial part, whose numerical value is obtained after the

calculation of the properties of the system.

(In the most common ab initio procedures for quantum mechanical calculations, Gaussian functions are used as basis

set. An Hartree-Fock iterative calculation is performed to

combine those basis functions into one-electron orbital).

107

then a conguration interaction (CI) is performed.

p

2E ,

of the excited states (actually the calculation provides

not the energy E ).

a small computational eort and with no need of perturbative

methods.

The SE for a N -electron free atom is:

"

where

1 2

p2

r

+ V0 (x) + V 0 (x) + 0 (x) = 0

2

2

N

X

r2 = r2j

j =1

V0 (x) =

and

V 0 (x) =

(3.2)

N

X

Z

j =1 rj

(3.3)

N

X

1

i>j rij

charge as Z .

(3.1)

(3.4)

p

2

0

108

The wavefunction is expanded by a linear combination of Slater

determinants

(x) =

where

C (x)

(x) =

p1 un ;l ;m ..;ms (x2 ) un ;l ;m ..;ms (x2 )

N!

.

.

un ;l ;m ;ms (xN ) un ;l ;m ;ms (xN )

(3.5)

x

x

un

un

( 1)

N ;lN ;mN ;msN

N ;lN ;mN ;msN ( 2 )

un

;l ;mN ;msN ( N )

..

.

N N

..

.

(3.6)

The one-electron functions un;l; m; ms (xj ) are the polar Sturmian orbitals given in Eq.(1.7), multiplied by the spin function (ms =

1=2); x stands for fx1; x2 ; : : : ; xN g and fxj g = frj ; #j ; 'j g.

Our basis set is not completely dened yet, because we have

to establish a rule for assigning a value to the exponents kj . We

demand our basis functions (x) to be a solution to the dierential

Equation [1, 8, 9, 11, 12]:

"

1 2

p20

r + V0(x) + 2 (x) = 0

2

(3.7)

(3.8)

n1 k1 = n2 k2 = ::: = nN kN = Z

(3.9)

and

109

Eqs.(3.8) and (3.9) imply that the exponents' value is:

kj =

p0

1

1

nj n + n + + n1N

q

2

1

2

2

(3.10)

relationship [8, 12]:

Z

2E

(3.11)

(x) is analogue to the denition of one-electron hydrogenic Sturmian functions: the energy ( p20 =2) is constant for all the functions,

while the `charge' plays the role of an eigenvalue.

We notice that the same Sturmian orbital may have dierent

exponents if it appears in two dierent congurations. For example,

p

in = 1s2 one has k1s = p0 = 2, while in = 1s2s one has

q

k1s = p0 = 5=4.

We have employed the unknown energy p20 =2 in the denition

of our N -electron basis set (Eq. 3.7). The exponents kj depend

on the value of p0 , i.e. on the value of the electronic energy (p0 =

p

2E ); consequently it looks like we are following an iterative

approach, in which we have to guess an initial value for p0 and then

iterate to get improved values for p0 until convergency is achieved.

Now we are going to show that actually using the basis set dened

in Eq.(3.7) doesn't imply any iteration: one has to calculate just

one matrix, and diagonalize it. Substitution of expansion (3.5) into

110

Eq.(3.1) yields:

X

"

p2

1 2

r

+ V0 (x) + V 0 (x) + 0 C (x) = 0

2

2

(3.12)

Then, taking into account that the functions (x) obey Eq.(3.7),

we can eliminate the kinetic energy operator from Eq.(3.12):

X

(3.13)

coordinates, exploiting Eq.(3.11) we obtain:

X Z

2E 0 ;

C = 0 (3.14)

denitions

1Z

T00 ;

dx 0 (x)V0 (x) (x)

(3.15)

p0

1Z

0

dx 0 (x)V 0 (x) (x)

(3.16)

T 0 ;

p0

T 0 ; T00 ; + T0 0 ;

(3.17)

we arrive to a concise expression for our secular problem:

X

[T 0 ;

p0 0 ; ] C = 0

(3.18)

Eqs.(3.11), (3.8) and (3.9):

0

11=2

X

2E

p

1

T00 ; =

0 ; = 0 0 ; = = @ kj2 A

p0

j

11=2

1A

0 ; = Z @

2

j nj

(3.19)

X

0 ;

111

The integral T00 ; doesn't depend on p0 's value, and this is true also

for the electronic repulsion integral T0 0 ; : in the radial part of the

integral, one can perform a change of integration variable from r to

p0 r, so that p0 's value is not needed to solve the integral. In order to

calculate energies and wavefunction for the electronic states of an

isolated atom, one has just to compute and diagonalize the matrix

T 0 ; .

The extension of the method exposed in the previous section to

include the eect of a strong electric eld is straightforward. We

have just to add a Coulomb interaction term in Eq.(3.1). If we

consider a constant electric eld of intensity E oriented along the z

axis, the interaction has the expression:

N

X

V 00 (x) = E rj cos #j

(3.20)

j =1

including in the Hamiltonian the potential in Eq.(3.20):

Xh

p0 0 ; C = 0

(3.21)

where

T000 ;

dx 0 (x)

N

X

j =1

p0 rj cos #j (x)

(3.22)

(3.23)

2

p0

112

The value of integral (3.22) is not a function of p0 . The procedure

for solving Eq.(3.21) is the following:

1. Establish a value for ;

2. Compute the matrix elements;

3. Diagonalize the matrix, getting p0 ;

4. The electric eld intensity is E = p20 ;

5. The energy of the atom in the electric eld is p20 =2.

In this section, the procedures for computing electronic integrals

involving Sturmian basis set are exposed. As we are dealing with

atomic systems there is no multicenter integral, consequently all

the formulas are analytical. At variance with Hartree-Fock orbitals,

Sturmian orbitals are not orthogonal to each other, so we have to

use generalized Slater-Condon rules [?]. In order to expose these

rules, we introduce the antisymmetrizer

X

A^ = ( 1)p P^

(3.24)

where the sum is extendend to all possible permutations of electrons, and p is the permutations parity.

113

3.4.1

Overlap Integrals

electron congurations

f1 (1) f2 (1)

f1 (2) f2 (2)

1

1

(x) = p F (x) = p

..

..

N!

N!

.

.

f1 (N ) f2 (N )

0 i between two N -

fN (1)

fN (2)

..

.

..

.

fN (N )

(3.25)

and 0 (x) = p1N ! G(x) similarly dened. The overlap can be expressed as:

h j 0 i = N1 ! hF j Gi

1 ^

hA[f1 (1) : : : fN (N )] j A^[g1 (1) : : : gN (N )]i

N!

= hf1 (1) : : : fN (N ) j A^[g1 (1) : : : gN (N )]i

hf jg i hf jg i hf jg i

1

1

1

2

1

N

hf2 jg1 i hf2 jg2 i hf2 jgN i

= ..

..

..

..

.

.

.

.

hfN jg1 i hfN jg2 i hfN jgN i

matrix whose elements are the overlaps between orbitals. In this

chapter we deal with atoms and exploit polar Sturmians so these

overlaps can be computed analytically. We have to solve the integral:

Z

un0 ;l0 ;m0 (r; #; ') un;l;m(r; #; ')r2 dr sin #d# d' =

= 23+2l (k

k

0 )l+3=2

"

(n l 1)!(n0 l 1)!

2n[(n + l)!]3 2n0 [(n0 + l)!]3

#1

2

(3.26)

114

Z

Z

The result of the angular integral is nl;n0 l0 , while the radial integral can be solved considering the explicit expression for Laguerre

polynomials:

Z

2

2

(n0 + l)!

n0X

l 1(

1)k

k!

k=0

nX

l 1 n0X

l 1

nX

l 1(

j =0

1)j

j!

n+l

n l j 1

n0 + l

n0 l j 1

(2k r)j 5

(2k r)k 5 dr =

( 2k )j ( 2k0 )k Z 1

dr exp (k +k0 )r r2l+2+j +k

j

!

k

!

0

j =0 k=0

The latter radial integral is easy to solve:

Z 1

(2l + j + k + 2)!

dr exp (k +k0 )r r2l+2+j +k =

(k + k0 )2l+j +k+3

0

Considering Eq.(3.10), one would expect the result of Eq.(3.26) to

be a function of p0 , but a deeper analysis indicates that a change of

variable could be performed inside the integral, from r to p0 r; this

implies the result to be independent from p0 's numerical value.

(n+l)!(n0 +l)!

3.4.2

form

V = v (1) + v (2) + : : : + v (N )

(3.27)

115

We want to obtain a general expression for the matrix element

h j V j 0 i. Considering the formulas given above, it is straightforward to show that

(3.28)

N N determinant F after deleting the rst row and the ith column.

We can expand the determinants F and G in terms of its minors:

F=

G=

N

X

( 1)i+1 fi (1)FiN 1

(3.29)

(3.30)

i=1

N

X

j =1

hF j v(1) j Gi =

N X

N

X

i=1 j =1

(3.28) can be made explicit in a very elegant form:

h j V j 0 i =

N X

N

X

i=1 j =1

(3.32)

where jSij j is the minor obtained from the determinant of the overlap matrix by deleting the ith row and the j th column.

If the operator in Eq.(3.27) is the Coulomb potential for an atom

embedded in a static electric eld (see section 3.3), then the matrix

116

element in Eq.(3.32) corresponds to the integral

Z

un0 ;l0 ;m0 (r; #; ') p0 r cos # un;l;m(r; #; ') r2 dr sin #d# d' =

Z

#1

"

(n l 1)!(n0 l0 1)!

0

2n[(n + l)!]3 2n0 [(n0 + l0 )!]3

0

0

exp (k +k0 )r rl+l +3 L2nl+1l 1 (2k r)L2nl0 +1l0 1 (2k0 r)dr

0

0

= 23+l+l kl+3=2 kl 0+3=2 p

Z

Yn0 ;l0 (#; ') cos #Yn;l (#; ') sin #d#d'

(3.33)

The radial part of this integral is very similar to the one in Eq.(3.26):

Z

0

0

exp (k +k0 )r rl+l +3 L2nl+1l 1 (2k r)L2nl0 +1l0 1 (2k0 r)dr =

2

0

exp (k +k0 )r rl+l +3 4(n + l)!

2

4(n0 + l0 )!

n0 X

l0 1 (

k=0

1)k

k!

nX

l 1

( 1)j

j!

j =0

n0 + l 0

n0 l 0 j

(2k

r )j 5

n+l

n l j

(2k

r)k 5 dr

nX

l 1 n0 X

l0 1

( 2k )j ( 2k0 )k Z 1

0

dr exp (k +k0 )r rl+l +3+j +k

j !k!

0

j =0 k=0

The solution of the latter integral is:

(n+l)!(n0 +l0 )!

3.4.3

(l + l0 + j + k + 3)!

0

dr exp (k +k0 )r rl+l +3+j +k =

(k + k0 )l+l0 +j +k+4

0

1

In this paragraph we are going to demonstrate generalized SlaterCondon rule for matrix elements between determinants involving

117

two-electron operators. The typical example of a two-electron operator is the Coulomb repulsion among N electrons, corresponding

to the sum of N (N 1)=2 terms 1=rij . If we dene the potential as

V0 =

1

j>i rij

(3.34)

1)

12

1

h

Fj

j Gi

2)!

r

12

(3.35)

We now expand the determinants F and G in terms of their double

minors:

F=

N X

N

X

fj (1)fi (2)]FijN 2

(3.36)

(3.37)

i=1 j =i+1

and

G=

N X

N

X

k=1 l=k+1

In Eq.(3.36), FijN 2 is the double minor obtained from the determinant F by deleting the rst and second rows and the ith and j th

columns. Considering that A2N 2 = (N 2)!AN 2 , and combining

Eqs.(3.35), (3.36) and (3.37), we get

N

X

h j V 0 j 0 i =

N X

N X

N

X

where

Cij ;kl =

1

[g (1)g (2)

r1 2 k l

118

and jSij ;klj is the determinant of the matrix obtained by deleting

ith and j th row, and kth and lth column from overlap matrix S .

From Eq.(3.39), we understand that in order to calculate the

matrix element given in Eq.(3.35), we have to solve integrals of the

tipe:

Z

1

dx1 dx2 un ;l ;m (x1 )un ;l ;m (x1 ) un ;l ;m (x2 )un ;l ;m (x2 )

r12

(3.40)

The operator can be expanded as [10]:

1

l

1 X

r<

4 X

1

=

r12 r> l=0 m= l r>

!l

1

Y (

)Y (

)

2l + 1 l;m 1 l;m 2

(3.41)

where Yl;m (

i ) are normalized spherical harmonics and

i = f#i ; 'i g.

Inserting the latter expansion into Eq.(3.40), and separating radial

and angular integrals (un;l;m(xj ) = Rn;l (rj ) Yl;m (

j )), we obtain :

1 Z

(

)

4

d

1 Yl;m (

1 )Yl ;m (

1 )Yl;m

1

l;m 2l + 1

X

(3.42)

d

2 Yl;m (

2 )Yl ;m (

2 )Yl;m (

2 )

3

r< l 1

r> r>

The integral of the product of three spherical harmonics is:

dr1 r12 Rn ;l (r1 ) Rn ;l (r1 )

1

v

u

u

t

3

(

)Y 0 0 (

)Y 00 00 (

) =

d

Yl;m

l ;m

l ;m

(2l0 + 1)(2l00 + 1)

hl; 0jl0; 0; l00; 0ihl0; m0; l00 ; m00jl; mi

4 (2l + 1)

(3.43)

119

So we can use Eq.(3.43) to solve the angular integral in Eq.(3.42),

that becomes:

4

l=max(jl

l j;jl l

min(l X

+l ;l +l )

2

(2l1 + 1)(2l + 1)

1

hl2 ; 0jl1 ; 0; l; 0ihl1 ; m1; l; mjl2 ; m2i

2

l

+

1

4

(2

l

+

1)

2

j)

(3.44)

(2l4 + 1)(2l + 1)

hl3 ; 0jl4 ; 0; l; 0ihl4 ; m4 ; l; mjl3 ; m3 iRn ;l

4(2l3 + 1)

1

;n ;l ;n ;l ;n ;l ;l

2

can be explicitly written as:

1

Z 1

Z r1

+1

1

0

rl

dr

Z 1

+2

l

dr2 r

2 Rn3 ;l3 (r2 )Rn4 ;l4 (r2 ) + r1

l

(3.45)

1

dr2 r

2

Rn ;l

16(f

4

Y

k

l3 1

3X

c

l1 1

1X

2f

1;3 )a

a!

=0

2+l+lX

3 +l4 +c+d

=0

1 l+lX

3 +l4 +c+d

i

=0

c

)

lk

c!

=0

2f

3;1

=1

(2fk )

1 + l1

n1

1 a

n

l

(nk

lk

nk (nk

l4 1

i1=2 n4X

lk )!

3 + l3

l3

c

2;4

2f

b

)

b!

=0

4 ;2 ) d

2f

d!

=0

h

l2 1

n2X

1)!

4 + l4

n4

l4

d

2 + l2

l2

b

1

(3.46)

(2 + l + l3 + l4 + c + d)!(1

l + a + b + l1 + l2 )!

3;1 + f4;2 )3+c+d+l+l3 +l4 (f1;3 + f2;4 )2 l+a+b+l1 +l2

(f

(2 + l + l3 + l4 + c + d)!(1

l + a + b + l1 + l2 + i)!

3 1 + f4;2 )3+c+d+l+l3 +l4 i (f1;3 + f2;4 + f4;2 + f3;1 )2 l+a+b+l1 +l2 +i

i!(f ;

3 4

j !(f3;1 + f4;2 )2 + 3 + 4 + +

(1

1 + l2 + a + b)!

4 2 + f3;1 )3+l+j+l1 +l2 +a+b

l + l + l + c + d)!(2 + l + j + L

l l l

c d j (f

; +f ; +f ;

13

24

fp;q

np n1q + n1p

2

(3.47)

120

denition of the basis set

We have chosen to use the energy of the atom, p20 =2, in the denition of the basis set (Eq. 3.7). It would be interesting to understand

whether this is the best possible choice for the denition of the basis set; perhaps a dierent value for the energy in Eq.(3.7) would

give a basis set that has better convergency properties. Let us try

and dene a basis set by the equation:

"

1 2 ~

p~2

r

+ V0 (x) + 0 ~ (x) = 0

2

2

(3.48)

In principle p~0 can take any value. If p~0 = p0 , the basis set ~ (x)

coincides with (x). Expanding the wavefunction by the basis set

dened in Eq.(3.48) and eliminating the kinetic energy operator as

in Eq.(3.13), we can transform the SE into:

X

"

p~20

2

(3.49)

coordinates, dividing by p~0 and considering Eq.(3.11), we get:

X

"

T; 0

p~

S 0

p~0 ; 0 + 0 S; 0 + ; E C = 0

2

p~0

(3.50)

The symbol S; 0 stands for the overlap between basis functions:

S; 0

(3.51)

121

Eq.(3.50) is a generalized eigenvalue problem, where the eigenvalue

is the energy E . We have to investigate which is the best value for

p~0 , and whether it coincides with p0 .

In the particular case of a single basis function ~ (x) (a trivial

1x1 matrix) our problem becomes:

p~0 E

+ =0

2 p~0

T;

(3.52)

p~2

E= 0

2

p~0 T;

(3.53)

The energy assumes the minimum value, T;

Exploiting Eq.(3.18) would give the same value for the energy, so

we conclude that in the particular case of a basis set made of one

function, the best value for p~0 is p0 .

For the more interesting case of a larger basis set, we are not

able to give any general proof, but considering a specic case we

demonstrated that the best value for p~0 is not always p0 . Let us

approximate the ground state of Helium atom by a linear combination of two functions: ~ 1 (x) = 1s2 (1 S ) and ~ 2 (x) = 1s2s(1 S ).

According to Eq.(3.50), the approximated ground state energy is

the lowest solution of the second order equation:

p~

E

2 + p~

T1;1

p~

T1;2 + 2 S1;2 +

0

S;

p~

1 2

0

T2;2

p~

2 + p~

0

=0

(3.54)

122

If we assign p~0 a value of 2.47 a.u., Eq.(3.54) gives E = 2:8557

a.u., while exploiting Eq.(3.18) one obtains p0 = 2:389 a.u. and

thus E = 2:8533 atomic units. This means that in general p0 is

not the best choice for the denition of the energy of the basis set.

3.6 Examples

When calculations over free atoms are performed using Eq.(3.18)

convergence rate toward the ground state energy is good, and moreover the upper eigenvalues give very good approximations to the

excited state energies. We performed a calculation over Helium (1 S

states), using a basis set made of 1 S bielectronic Sturmian functions with quantum numbers up to n1;max = 4; l1;max = 2; n2;max =

10; l2;max = 2. Accurate 1 S states for helium are available since

long time [13], and continue to be a benchmark for alternative basis sets in variational calculations [14,15]. The ground state energy

we have obtained is 2.902690 a.u., to be compared with the best

variational value 2.903724377 a.u. (error = 0:036%). Considering

also upper eigenvalues, we have been able to reproduce carefully

by our ab initio calculation the Helium 1 S electronic transition

energies between the ground state and several excited states (Table

3.1). In the literature there are some recent examples of accurate

calculations on Helium excited states [16, 17] performed with various methods, but they seem to be not suitable for extensions to

more complex atoms.

123

1 S Levels

1s2

1s 2s

1s 3s

1s 4s

1s 5s

1s 6s

1s 7s

Calculated(a)

(a.u)

-2.902690

-2.147417

-2.061402

-2.033607

-2.021181

-2.014546

-2.010585

(b) NIST Atomic

bin/AtData/main

Transition energies

1s ns 1s2 (cm 1 )

165763

184641

190742

193469

194925

195794

Spectra Database

asd).

Experimental(b)

166277.547

184641.369

190741.633

193468.726

194924.965

195794.328

(http://physics.nist.gov/cgi-

electronic transition energies can be shown to be a general feature,

and was tested also on atoms having more than two electrons [8,12].

We have tested the Sturmian method also for a preliminary calcualation of the static polarizability of Lithium 2 S ground state,

working with a minimal basis set (1s2 2s, 1s2 2p, 1s2 3s, 1s2 3p). We

calculated the energy E of the free atom and the energy E 0 of the

atom in the presence of a 10 5 a.u. electric eld (E ). Then exploiting the approximated relationship that links the energy dierence

to the static polatizability zz

1

E0 = E

E

(3.55)

2 zz

we obtained for zz the result of 25:0 10 24 cm3 , to be compared

with the experimental value of 24:3(0:5) 10 24 cm3 given in the

124

literature [18].

Bibliography

[1] O. Goscinski, Preliminary Research Report No. 217, Quantum

Chemistry group, Uppsala University (1968).

[2] J. Avery,

[4] J. Avery and D.R. Herschbach, Int. J. Quantum Chem., 41,

[3] J. Avery,

673 (1992).

(1997).

Grossi, Int. Rev. Phys. Chem., 20, 673 (2001).

[7] J.P. Gazeau and A. Maquet,

[8] J. Avery, Hyperspherical Harmonics and Generalized Sturmians. Kluwer Academic Publishers, Dordrecht, The Netherlands

(2000).

[9] V. Aquilanti and J. Avery,

Molecules. Academic Press, New York, 1975.

125

[12] V. Aquilanti and J. Avery, Adv. Quantum Chem., 39,

[11] J. Avery,

71

(2001).

[14] A.J. Thakkar and T. Koga, Phys. Rev. A, 50, 854 (1994).

[15] S.P. Goldman, Phys. Rev. A, 57, 677 (1998).

[16] G.W.F. Drake and Zong-Chao Yan, Chem. Phys. Lett., 229,

[13] C.L. Pekeris,

486 (1994).

4755 (1998).

J. Phys. B, 31,

[18] R.W. Molof, H.L. Schwartz, T.H. Miller and B. Bederson Phys.

Rev. A, 10, 1131, 1974.

126

Chapter 4

Sturmian approach to one-electron

many-center systems: integrals and

iteration schemes

Summary

for nuclear attraction integrals involving both the polar and the

parabolic (or Stark) Sturmian set (see Sec. 1.2). These integrals are

needed for the matrix elements entering the secular problem for the

construction of molecular orbitals within the Born-Oppenheimer

scheme. Such a secular problem can be formulated at dierent iteration levels for the one-electron Schrodinger equation, and their relative performances against truncation are quantitatively assessed.

127

128

4.1 Introduction

Shibuya and Wulfman rst proposed the use of suitably normalized

Coulomb orbitals as basis sets for one-electron molecules in quantum chemistry, exploiting the momentum space approach [1], where

these orbitals are related to hyperspherical harmonics. Later, this

matter was further developed by other researchers [2, 3, 8, 10{13,

19,23{27] who when working in conguration space generally refer

to these orbitals as Sturmians. In the literature there are also recent and extensive reviews and books [4, 20, 30]. By means of this

method, the Schrodinger equation is trasformed into an algebraic

eigenvalue problem, whose matrix elements are linear combinations

of nuclear attraction integrals (NAIs) involving Sturmians. Actually, it is possible to formulate the algebraic problem according to

dierent levels of iterations, which are not equivalent when using

a nite-size basis set, as necessary when truncation is applied in

explicit calculations. The most extensive results on the electronic

energy of H+2 were obtained by Koga and Matsuhashi, who demonstrated the extreme accuracy of the Sturmian method [13].

In Sec. 4.2 we reconsider the basic integrals S and W [1], for

polar and parabolic Sturmians; in Sec. 4.3 we show examples of calculations for H+2 in order to demonstrate that the Sturmian method

yields satisfactory accuracy also in the case of a small-size basis set,

and then we report a quantitative comparison among the performances of the dierent iterations of the wave equation.

129

We recall that Sturmians orbitals are dened in conguration space

as the set of functions f (x) which solve the equation

1 2 1 2

r + 2 p0

2

np0

f (x) = 0

r

(4.1)

quantum numbers: the usual principal quantum number n is the

rst of the set, and the others depend on the coordinates chosen to

separate variables in Eq.(4.1). This can be done in four types of

coordinate systems (polar, parabolic, spheroidal, spheroelliptic; see

Chapter 1) [31]. Further alternatives are available in momentum

space (chapter 2); see [28,32] for a classication. In this chapter we

only deal with NAIs involving polar (unlm) and parabolic (Unm )

Sturmians, which permit closed form treatments. Denitions and

relationships between these two alternative Sturmian basis sets can

be found in Ref. [21]. These Sturmian hydrogenic sets obey a peculiar orthonormality condition:

nZ

1

dx f0 (x) f (x) = 0 ;

p0

jxj

(4.2)

An explicit expression for the integral [4]

nZ

R) = p0 dx unlm(x) jx1j un0l0m0 (x

n0 l0 m0 (

Snlm

R)

(4.3)

130

(R is the distance between the two centers) can be obtained working

in momentum space and exploiting angular momentum quantum

theory [1]. The following form for the integral is essentially due to

Dunlap [2]; we have rederived it according to our phase conventions

for the orbitals [21]:

n0 l0 m0 (

Snlm

R) = (

0

)l l+M 2

p30

8 0

n

>

>

< 2

:

v

u

1

n0 1

2

l0

N;L

9

n 1

2

n 1

N 1 >

=

2 >

N 1

[

>

>

;

R)

NLM (

L)(N + L + 1)

1u

t (N

N +1;LM (R)

2

N (N + 1)

v

u

u

t

1 (N + L)(N L

2

N (N 1)

Here,

M

8

9

1)

N 1;LM (R)5

>>=

> is a 9j symbol.

>

>

: >

;

>

>

<

n l m (R) =

Wnlm

00 0

1Z

1

dx unlm (x)

p0

jx Rj un0l0 m0 (x)

(4.5)

explicit expression has been published yet. Exploiting the expansion [4]

jx

1 r

1 X

<

=

x0 j r> l=0 r>

!l

4 X 0

Y (^x )Ylm (^x)

2l + 1 m lm

(4.6)

131

n0 l0 m0 (R):

we have obtained the following expression for the integral Wnlm

"

0 0

0 0

R) = 2 (n + l)!(n + lnn)!(0n(2l +l 1)(21)!(l00n+ 1)l

n0 l0 m0 (

Wnlm

l00

#

1)!(2l0 + 1) 1=2

Yl00 m00 (R

(4.7)

nX

l 1

( 1)j

j =0 j !(2l + j + 1)!(n l

n0 X

l0 1

( 1)k

0

0 l0

k=0 k !(2l + k + 1)!(n

1)!

(l + l0 + l00 + j + k + 2)!

1)!

(2s)l00 +1

2l00

a l00 1

2s (l + l0 + l00 + j + k + 2)! X (2s)

+ e 2s

a

!

a=0

00 +j +k+1 "

l+l0 lX

b=0

(l + l0

l00 + j + k + 1)!

b!

depend on s, not on R: this means that the we have to pick a value

for s, solve the secular equation to get p0 , and eventually obtain

the physical distance R as s=p0 . For R = 0 both (4.3) and (4.5)

reduce to (4.2). Furthermore, it can be shown that [1, 8]:

0

W =

00

=

(l + l0 + l00 + j + k + 2)

b+l00

(2

s

)

;

(b + 2l00 + 1)!

00 1

00

S 00 S0

n

(4.8)

for direct calculation of W0 (see however next section).

When using parabolic Sturmians as a basis set for the oneelectron multicenter systems, we have to evaluate S and W integrals

132

involving those functions. In Ref. [21], the question of the evalun0 0 m0 was tackled expanding parabolic functions by the

ation of Snm

polar ones, and then exploiting the result in Eq.(4.4). Here we show

n0 0 m0 is studied directly

the result that is obtained when integral Snm

in momentum space, according to Shibuya and Wulfman's spirit:

n m (R) =

Snm

0 0 0

1

nZ 3

dx Unm (x) Un0 0 m0 (x

p0

jxj

R) =

(4.9)

!

nn0 1=2 X n 1 + m n0 1 0 + m0 n00 1 00 + m00

=2

h 2 ; 2 ; 2 ; 2 j 2 ; 2 i

p30

n00

h 2 ; 2 ; 2 ; 2 j 2 ; 2 i n00 fUn00 00 m00 (R)

2v

u

00

1 4u

00 )2 m002

t (n + 1

Un00 +1;00 1;m00 (R)

4

n00 (n00 + 1)

v

u

u

t

v

u

u

t

v

u

u

t

(n00

1 + 00 )2 m002

Un00 1;00 1;m00 (R)+

n00 (n00 1)

Un00 +1;00 +1;m00 (R)

n00 (n00 + 1)

(n00

39

=

1 00 )2 m002

5

00

00

00

U

(

R

)

n

1

;

+1

;m

;

n00 (n00 1)

00 + 0 .

0 m0

n

The integral Wnm in the parabolic basis set is introduced

in this work for the rst time. For its evaluation, the potential is

expanded according to Eq.(4.6), and then the parabolic coordinates

appearing as variables in the Sturmians Unm are transformed into

n0 0 m0 is solved in

polar coordinates r; ; , so that the integral Wnm

polar coordinates. The integrations over r and are easy; for the

integration over , the spherical harmonic Yl00 ;m00 (; ) is expressed

133

in terms of a Jacobi polynomial (Ref. [17], page 138); then the

integration over is performed by Eq. 7.391(2) of Ref. [18], yielding

a generalized hypergeometric series 3 F2 (1); the latter is replaced by

a Clebsch-Gordan coecient, according to Eq.(22) at page 241 of

Ref. [17]. The nal expression is easily programmable in Fortran

or in Mathematica language:

Z

0 0 0R

n m

Wnm

n+

nn0

= 2

0

n + 0

n m

2

X

a

0 +0

2

X

c

1)

c!(c +

m0

)!

^

Yl00 ;m00 R

1)

"

0 +0 1

2

00

(2l

00 +1

(2s)l

( +

00

+ 2)!

a

;

b+c

2s

+ 00 +2

X

l

=0

( +

00

i!

+ 0

2

b+d+ m m

00

00

m0

i1=2

1)

n m

1)

)!

+ 0 +m00 ! a + c + m+m0

2

2

( + l00 + 1)!

( + 1)(

d!(d +

a+c+ m m

+ 1)

+ 0 +m00 !

2

+m

0 1

=0

hl00 ; m00

2

X

(4.10)

0

n

b!(b + m)!

0 0

=0

2

X

+ 1

2

"

n++m

n m

a!(a + m)!

( ) =

0

n + 0 + m0

b+d+ m m

x jx Rj Un00 m0 x

n m

(

=0

00

0 1

X

=0

dx Unm (

0

n

) =

0 0 1

2

00

00 #1=2

)!

a

;

#

+ 2)!

(2s)

00

b+c

d+m

2

X

l00 +1

00

s l e 2s

j =0

(2 )

(

00

j!

)

+ 1)!

(2s)

the simplest cases of the integral in Eq.(4.10) are given in Table

n0 l0 m0 integrals (Eq.4.5) can be found in

4.1. The analogue for Wnlm

Refs. [4, 16].

134

Table 4.1: Nuclear attraction integrals W involving parabolic Sturmians, Eq.(4.10).

n; ; m n0 ; 0 ; m0

1,0,0

1,0,0

1,0,0

2,-1,0

2,1,0

2,-1,0

1

n0 0 m0 (R) = 1 R dx3 U

Wnm

nm (x) jx Rj Un0 0 m0 (x)

p

1 e s (1 + s)

s

s

0

1,0,0

2,-1,0

2,1,0

2,-1,0

2,1,0

2,1,0

2 s+e

(2+5

p s+6s +4s )

2 s 2s

2 s e p(2+3s+2s )

2 2s

3+3s+2s e s (3+9s+14s +13s +8s +4s )

2s

3 3s+2s e s (3+3s+2s +s )

2s

3+e s (3+6s+6s +4s +2s )

2s

2s

performances of dierent iterations

Let us consider the Schrodinger equation for one electron in the

presence of several xed nuclei, that will be labeled by index a. We

require that all functions in the set have the same exponent p0 , and

constrain this exponent to the (unknown) electron energy p20 =2.

Expanding the wavefunction by Sturmian orbitals centered on the

nuclei, one has:

X

"

p2

1 2

r

+ v (x) + 0 c f = 0

2

2

(4.11)

v (x) =

va (x) =

Za

jx Xaj

(4.12)

135

Exploiting Eq.(4.1), and dividing Eq.(4.11) by p0 , one obtains the

generalized eigenvalue problem [4, 9]:

X

(A; 0

p0 C; 0 ) c = 0

(4.13)

where

1Z 3

dx f 0 (x)v (x)f (x)

p0

n Z 3 va (x)

C; 0 =

dx f 0 (x)

f (x)

p0

Za

A; 0 =

(4.14)

(4.15)

the example discussed in this chapter, applications of the Sturmian

method are referred to a one-electron molecule with nuclear charges

Z1 and Z2 . In this case, one has (subscripts 1 and 2 refer to the

two nuclei) [4]:

Z1

0

;0 + Z2 W (R)

0

n

Z1 Z2 0

+

S (R)

Af1;g;f2;0 g =

n n0

Cf1;g;f1;0 g = ;0

0

Cf1;g;f2;0 g = S (R)

Af1;g;f1;0 g =

(4.16)

(4.17)

(4.18)

(4.19)

any two-center one-electron molecule. We have considered H+2 , for

which Z1 = Z2 = 1. Sturmian orbitals have the correct exponential

behavior on the nuclei, thus noticeable accuracy can be achieved

using a small basis set, as can be seen in g.(4.1).

136

-0.6

-0.8

{1s}

-1

{1s, 2s}

-1.2

E ( = - p0 / 2 )

-1.4

-1.6

-1.8

-2

R ( = s / p0)

Figure 4.1: Energy of the electron ground state in H+2 . The circles

stand for the 10-gure accuracy data by Koga et al. [13]. The three

curves represents the results of Eq.(4.13) for three dierent polar basis

sets: f1sg; f1s; 2sg; f1s; 2s; 2pz g.

137

As it is clearly demonstrated in Ref. [4], there is an interesting

relationship between matrix elements A; 0 and C; 0 , which could

not be gured out at a rst glance but is connected to Eq.(4.8):

A; 0 =

00

Z 00

C; 00 00 C 0 ; 00

n

(4.20)

This allows a simpler form for obtaining eigenvalues and eigenvectors of the one-electron system [4, 9]

X

0s

@

Za Za0

A 0

nn0 ;

; 0 p20 A c = 0

(4.21)

An even simpler form was given by Novosadov [23] (see also [2]):

X

0s

@

Za Za0

C 0

nn0 ;

; 0 p0 A c = 0

(4.22)

and third iteration of Eq.(4.22). In the limit of an innite basis set, Eqs.(4.22), (4.21) and (4.13) would be equivalent, while

when a nite expansion is exploited, Eq.(4.13) is more accurate

than Eq.(4.21), which in turn is more accurate than Eq.(4.22). The

reason is that the A matrix elements can be computed directly and

analytically, as linear combinations of S and W : otherwise, if we

were going on to utilizing Eq.(4.20) for the calculation of A truncating the summation according to a chosen dimension for the basis set,

the three equations would be exactly equivalent. It is interesting

to provide a quantitative comparison of the dierent performances

of equations (4.13), (4.21) and (4.22) over H+2 . For the solution of

138

eigenvalue problems and generalized eigenvalues problems, we have

used Lapack libraries written in Fortran, available on the Internet.

Fig.(4.2) clearly demonstrates that Eq.(4.13) is much more convenient than the others. In order to obtain more accurate results

than those reported in Fig.(4.2) for Eq.(4.13) by enlarging the basis set, we encountered problems of a computational nature, due to

excessive closeness to zero of some elements of the C matrix. These

diculties can be interpreted as an indication of the tendency of

the basis set towards overcompleteness [16], when its dimension is

increased: in other words, since C matrix can be viewed as an overlap matrix in a Sobolev space [33], zero eigenvalues are signatures

for linear dependence among functions in the basis set.

The most direct way for avoiding such a problem was proposed

by Lowdin and others [14, 15], who suggested to proceed with an

expansion of the molecular orbital in terms of a complete set centered on a single point in the space, which will be the midpoint in

the H+2 case. It is interesting to explore the suggestion, inserting

such a single-point expansion in Eq.(4.11): one obtains the secular

problem:

Xh

nl

00

0 0i

n l m (s=2) k n l c

2Wnlm

nl

nlm; = 0

(4.23)

out to be split in two blocks because of the symmetry of H+2 : indeed, the sum involves only even l's for gerade states, and only odd

l's for ungerade states. Results obtained by solving Eq.(4.23) are

139

-1

1.0010

1.0010

-2

first iteration

1.0010

1.0010

-3

second iteration

-4

1.0010

1.0010

-5

third iteration

-6

50

100

iterations of the wave equation [rst order, Eq.(4.22); second order,

Eq.(4.21); third order, Eq.(4.13)]. Data refer to H+2 , for an internuclear

distance of 2 a.u.; polar Sturmians were used as basis set. The absolute

error in atomic units is computed with respect to the benchmark results

by Koga et al. [13].

140

given in Fig.(4.3). As the internuclear distance increases, a larger

and larger basis set would be necessary to approximate correctly

the H+2 wavefunction, and one should face the problem of computn0 l0 m0 matrix elements for high quantum numbers, but the

ing Wnlm

accuracy obtained at such an elementary level is most encouraging.

This chapter has considered the calculation of integrals which appear on matrix elements for one electron multicenter problems in

the Sturmian approach. A brief investigation has also been carried out to assess the relative eciencies of alternative iteration

schemes, where these integrals play a role. Relative merits of the

polar versus parabolic basis need to be studied more extensively

(for some preliminary results, see [21]).

In the perspective extension of the use of Sturmian sets to the

solution of molecular problems of increasing complexity, it is important to develop ecient algorithms for the computation of bielectronic multicenter repulsion integrals, treated in the next paper.

To this aim, we note that the Sturmian orbitals can be written as

linear combination of Slater-type orbitals (STO): therefore, results

and codes developed for the calculation of integrals between STO

(for example see Refs. [5{7]) can be usefully employed for carrying

out calculations by the Sturmian approach: test cases for molecules

are discussed elsewhere [35].

141

-0.6

-0.8

-1.2

E = - k /2 (a.u.)

-1

-1.4

-1.6

-1.8

-2

2

R = s / k (a.u.)

Figure 4.3: The circles stand for the 10-gure accuracy data by Koga

et al. [13]. The three curves represents the results of Eq.(4.23) for three

dierent basis sets: fnmax ; lmax g = f3; 2g; f6; 5g; f8; 6g.

142

Bibliography

[1] T. Shibuya and C.E. Wulfman,

(1965).

[2] Brett I. Dunlap

Molecules. Academic Press, New York (1975).

for Diatomic

[4] J. Avery, Hyperspherical Harmonics and Generalized Sturmians. Kluwer Academic Publishers, Dordrecht, The Netherlands

(2000).

[5] J.F. Rico, R. Lopez and G. Ramrez,

(1988).

Phys. Commun., 64, 329 (1991).

[7] J.F. Rico, R. Lopez, I. Ema and G. Ramrez,

Commun., 105, 216 (1997).

[8] T. Koga,

Comp.

Comp. Phys.

143

[13] T. Koga and T. Matsuhashi, J. Chem. Phys., 89, 983 (1988).

[14] H. Shull and P.-O. Lowdin, Svensk Kem. Tidskr., 67, 373

[12] T. Koga and T. Matsuhashi,

(1955).

[16] J. Avery and R. Shim, Int. J. Quantum Chem., 83, 1 (2001).

[15] K.M. Howell and H. Shull,

Quantum Theory of Angular Momentum. World Scientic,

Singapore, 1988.

[18] I.S. Gradshteyn and I.M. Ryzhik. Table of Integrals, Series

and Products. Academic Press, New York, 1980.

[19] J. Avery, Hyperspherical Harmonics, Applications in Quantum

Theory. Kluwer Academic Publishers, Dordrecht, The Netherlands (1989).

[20] J. Avery,

Phys., 209, 405 (1996).

[22] V. Aquilanti, S. Cavalli and C. Coletti,

(1997).

[23] B.K. Novosadov

Chem.

144

[24] Ch. Duchon, M.Cl. Dumont-Lepage and J.P. Gazeau, J. Phys.

A, 15, 1227 (1982).

[25] Ch. Duchon, M.Cl. Dumont-Lepage and J.P. Gazeau, J. Chem.

Phys., 76, 445 (1982).

[26] H.J. Monkhorst and B. Jeriorski,

(1979).

[27] V. Aquilanti and J. Avery,

3209 (1998).

Grossi, Int. Rev. Phys. Chem., 20, 673 (2001).

[30] V. Aquilanti and J. Avery,

(2001).

Chem., 92, 99, (2003).

Int. J. Quantum

Quantum Chem., 92, 212, (2003).

[33] E.J. Weniger

71

Int. J.

145

Kryachko (Eds.), 2003 Kluwer Academic Publishers.

146

Chapter 5

Sturmian Orbitals Applied to

Molecules: an Introduction

Summary

chemical problems is the conguration space counterpart of hyperspherical analysis in momentum space and leads to promising algorithms alternative to the usual SCF-plus-conguration interaction

hierarchies. In this chapter we introduce the basic steps of a computational scheme for molecular structure problems, where Sturmian

orbitals appear as building blocks in a valence-bond type of approach. The example is the hydrogen molecule. The mathematical

ingredients are considered, particularly the possibility of exploiting

relationships with Slater-type orbitals in order to circumvent the

bottleneck of calculation of matrix elements.

147

148

5.1 Introduction

Being the Schrodinger equation (SE) for the non-relativistic hydrogen atom analytically soluble in a closed form, the use of hydrogenoid orbitals as basis sets to approximate the wave functions

of atoms and molecules has been extensively considered since the

early days of quantum mechanics. Slater-type orbitals (STO) and

other variants have been proposed and amply tested as alternatives. In order to tackle the obstacles encountered for the ecient

computation of matrix elements (specically the bielectronic integrals), preference has been given to the Gaussian orbitals (GTO),

particularly convenient for such purposes.

and molecular properties, typically exploiting Gaussian basis set

expansions, almost invariably initiate with Self Consistent Field

(SCF) or Multiconguration Self Consistent Field (MC-SCF) calculations yielding molecular orbitals as linear combinations of GTO

centered on the various nuclei of the molecule, and then proceed

with post-Hartree-Fock techniques (Conguration Interaction, Coupled Clusters, ...). Among the disadvantages of such a procedure,

we mention the diculties encountered in the calculation of longrange interactions and of the properties of excited states, and the

slow convergence in reproducing the cusps in the electronic densities

at nuclei.

The Sturmian orbitals can be straightforwardly expressed as

149

linear combinations of Slater-type orbitals. The use of the latter

has been superseded by the GTO, for which the slower convergence is often amply balanced by the much simpler algorithm for

the calculation of integrals. Apart from this, the employed techniques are identical. The approach involving Sturmian orbitals will

be shown to proceed along a route fully alternative to modern ab

initio quantum chemistry: it will be seen that there is no need of

iterative Hartree-Fock calculations, because the introduction of the

Sturmian expansion of the electronic wave function leads after algebraic manipulations to a generalized eigenvalue problem (GEP)

where the matrix elements contain mono- and bi-electronic integrals

among Sturmian orbitals and the eigenvalue is not the electronic

energy E but the momentum wave number p0 such that E = p20 =2

(atomic units are implied). The typical integrals of quantum chemistry depend explicitly on the nuclear coordinates Ri , while in the

Sturmian approach parameters si = p0 Ri appear. The basis feature

is therefore that the Born-Oppenheimer separation is not settled before the calculations. The si parameters are instead xed and only

after the solution of the GEP from the relationships Ri = si =p0 one

nds out what is the point in the potential energy surface which

corresponds to an energy p20 =2. Another unusual property of this

approach is that the eigenvalues obtained by solving the GEP come

out as correct solutions not only for ground states, but also for the

excited states corresponding to the same symmetry.

We consider the application of the Sturmian orbital procedure

150

to the ab initio quantum chemistry of molecules as many-electron

many-nuclear systems. The recent proposal, as reviewed in Avery's

book [10, 32], involves a MO-LCAO approach where one-electron

molecular orbitals are computed rst, and then their products are

employed to build-up N -electron congurations. Such an approach

is currently being implemented, one diculty being the recovery

of the Born-Oppenheimer separation, because, as indicated above,

the matching of si parameters and Ri coordinates occurs through

scaling by the eigenvalues p0 .

This chapter presents an account of a promising method for the

application of the Sturmian orbital approach to molecular structure calculations. The new proposal (Sec.5.2.1) for the extension of

generalized Sturmian sets to molecular structure is founded on concepts and formalisms previously elaborated. In the framework of

quantum chemistry jargon, it will be recognized as a valence-bond

type of approach: the calculation of the potential energy curve for

the H2 molecule provides encouraging results already at the level

of minimal basis sets. Sec.5.2.2 is devoted to a discussion of the

practical obstacles to the implementation of this approach, the calculation of integrals, which can be in part circumvented through

the angular momentum algebra applicable in the momentum space

perspective, and in part tackled by exploiting the connections with

STO and the existence of programs dealing with integrals involving

the latter. Conclusion are in Sec.5.3.

151

molecular calculations

There are four dierent coordinate systems (polar, parabolic, spheroidal

and spheroelliptical) which allow separation and solution of the partial dierential equation (4.1): we can associate to each of them a

Sturmian basis set corresponding to alternative symmetry properties [21] (Chapter 1). For deniteness, here we will only deal with

the most common one of these sets, which employs polar coordinates (r; #; ').

5.2.1

for the study of systems having many nuclei and electrons. The

SE for a molecule coincides with Eq.(3.1), provided that we dene

V0 (x) according to

N

X

XX

Za

(5.1)

V0 (x) = V0;a (x) =

a i=1

jxi Xaj

functions (x) are dened by an equation analogous to Eq.(3.7):

"

#

1 2

p20

z

r + Vp (x) + 2 (x) = 0

(5.2)

2

The potential Vpz (x) is the sum of N contributions, each of them

representing the interaction of one electron with one of the nuclei:

N

X

Zp;j

(5.3)

Vpz (x) =

j =1

jxj Xp;j j

152

This means that actually there is not only one equation dening the

basis set, because there are many choices for Vpz (x): the basis set

can be divided into several subsets, each of them associated to an

equation like (5.2) having a dierent Vpz(x). A function (x) is a

determinant of Sturmian orbitals u (x Xa ) like Eq.(3.5), provided

that two subsidiary conditions are satised: the rst one is Eq.(3.8),

and the second is a modication of Eq.(3.9) taking into account

that in general Sturmian orbitals appearing in the determinants

are centered on the dierent nuclei of the molecule:

=

=

= =

Za0

Za0

Za00

(5.4)

=

p0

+

(5.5)

since we perform CI over congurations which are products of nonorthogonal atomic orbitals. In order to clarify the concepts exposed

and show how this method works in practice, we will show an application to the simplest molecule: H2 . The crudest approximation

to the ground state 1 g wavefunction is:

g (x1 ; x2 ) =

1

2

(5.6)

153

In this case the basis set is constituted by two bielectronic functions;

1 (x) = 1sA(1)1sB (2) corresponds to the potential

V1z (x) =

(5.7)

V2z (x) =

(5.8)

nuclei as:

V0 (x) = V1z (x) + V2z(x)

(5.9)

According to Eq.(1.7), 1s Sturmian orbitals are dened as

!

k3 1=2

1s(1) =

e

k r

(5.10)

p

it is p0 = 2. In general, the exponent of an orbital will depend

on the principal quantum numbers of all the orbitals forming the

conguration (x) in which it appears.

Now we will calculate an approximation to H2 electronic energy

exploiting the wave function (5.6). Entering Eq.(5.6) inside (3.1)

and writing the potential V0 (x) as in Eq.(5.9) one can obtain the

1x1 secular problem:

Z

"

#

(5.11)

1 2

1 p20

z

z

r + V1 (x) + V2 (x) + r + 2 1sA(1)1sB (2)d1d2 = 0

2

12

154

The latter expression can be simplied with the aid of Eq.(5.2):

Z

(5.12)

1

(1 1 )V1z (x) + V2z(x) +

1sA (1)1sB (2)d1d2 = 0

r

12

Taking into account that the basis set functions associated to the

same operator Vpz (x) enjoy potential weighted orthonormality relationships

Z

2E

dx 0 (x)Vpz(x) (x) = 0 ;

(5.13)

we can modify Eq.(5.12) as follows:

Z

1

2E

z

2E + 1sA(1)1sB (2) V2 (x) +

1s (1)1sB (2)d1d2 (5.14)

1

r12 A

+ 1sB (1)1sA(2) (1

1

z

z

1 )V1 (x) + V2 (x) +

1sA (1)1sB (2)dx = 0

r12

If we write down all the integrals explicitly and exploit Eq.(5.5),

we can rewrite Eq.(5.14) as:

2p0 +p0

1s2B (2)d2

1s2A (1)

jx1 XB j

d1

1s2A(1)d1

+(1

"

"

Z

jx2 XAj d2

d1d2

+

r12

Z

Z

1sA (1)1sB (1)

1sA (2)1sB (2)d2

d1

Z

pp0 )

2

1s2B (2)

jx1 XAj

jx2 XB j d2

jx1 XB j d1

(5.15)

155

Z

1sA(2)1sB (2)

jx2 XAj d2

d1d2 = 0

r12

Eventually, we divide the latter by p0 and write the NAI's in a

more compact form, exploiting the denitions (4.3) and (4.5). The

expression for the eigenvalue is:

+

"

p0 =

2+

100 (s) + 1

2W100

p0

d1d2+

r12

(5.16)

#

h

i

p

1 Z 1s2A (1)1s2B (2)

100 (s) = 1 + M100 (s)S 100 (s)

d1d2 2 2M100

(

s

)

S

100

100

100

100

p0

r12

The M's are two-center overlap integrals between Sturmians:

Z

0 l 0 m0

Mnnlm

un0l0m0 (x)unlm(x)dx

For example,

1

M100

100 = 3 e

s (3 + 3s + s2 )

(5.17)

(5.18)

We can show (see Appendix) that these M integrals can be evaluated in momentum space exploiting angular momentum algebra,

analogously to the case of the S integrals encountered in Chapter

4.

Although p0 is in the denition of the exponent k , mono- and

bi-electronic integrals in Eq.(5.16) actually do not depend on the

value of p0 : rather, they depend on the product s = k R (R

being the internuclear distance). Therefore, we pick up a value for

s, compute the matrix elements and then we can get the eigenvalue

156

p

2s=p0 .

Results on the potential energy curve for the ground state of

H2 , calculated by this procedure, are reported in Fig.(5.1). Even

if really minimal, the basis set of Eq.(5.6) gives a good qualitative

picture of the chemical bond: the equilibrium distance is close to the

real one, and the asymptotic behavior is correct. A more elaborate

calculation is also shown in Fig.(5.1). We have tested that even

modest size calculations employing larger basis sets yield accurate

results also for excited states.

5.2.2

chemical methods, because it can involve large eorts in terms of

computer times and therefore may limit the concrete possibility of

extending the calculations to cover complex systems. This discussion will pertain specically to the mono- and bi-electronic integrals

encountered in Sec.5.2.

Generally, the use of a basis set as dened in Eq.(5.2) leads to

monoelectronic integrals S ; W and M containing two orbitals which

can dier in the exponents appearing in Eq.(1.7). This represents

a limit for the application of momentum space harmonic analysis, at least according to its present developments. To circumvent

this bottleneck and yet be able to test the perspective power of

157

-1

V(R) (a.u.)

-1.05

(c)

-1.1

(b)

-1.15

(a)

3

R (a.u.)

ab initio potential

energy curve for H2 denoted as (a), and the Sturmian approach. Curve

(c) corresponds to the single conguration function in Eq.(5.6) and curve

(b) has been obtained including in the expansion all congurations from

all Sturmian orbitals up to 3d. In the latter case, the variance in the

energy minimum with the one given in [28] is +0.3%.

158

R (a.u.)

1

1.2

1.3

1.39

1.4

1.4011

1.5

1.6

1.8

2

2.2

2.4

2.6

2.8

3

3.2

V(R) (a.u.)

-1.1245388

-1.1649344

-1.1723462

-1.174452

-1.1744748

-1.174475

-1.1728541

-1.1685821

-1.1550675

-1.1381316

-1.1201304

-1.1024201

-1.0857874

-1.0706776

-1.0573174

-1.0457865

159

R (a.u.)

1.0821753

1.2020791

1.3254692

1.4521964

1.5820863

1.7149417

1.8505432

1.9886483

2.1289914

2.2712856

2.4152266

2.560499

2.7067849

2.8537741

3.0011745

3.1487233

3.2961955

3.4434107

3.590235

3.7365797

V(R) (a.u.)

-1.1423625

-1.1611956

-1.1694278

-1.1701995

-1.1657679

-1.1577794

-1.1474508

-1.1356935

-1.1231972

-1.1104875

-1.0979637

-1.0859263

-1.0745945

-1.0641206

-1.0545992

-1.046076

-1.0385553

-1.0320072

-1.0263758

-1.0215866

160

R (a.u.) V(R) (a.u.) R (a.u.) V(R) (a.u.)

0.7290924 -0.90468312 2.6097341 -1.0278317

0.80695213 -0.97216731 2.7124688 -1.0231117

0.88703841 -1.0204927 2.8151786 -1.0188752

0.96934499 -1.0543036 2.9178118 -1.0151008

1.0538422 -1.0770535 3.020328 -1.0117613

1.1404765 -1.0913646 3.1226974 -1.0088259

1.2291706 -1.0992606 3.2248993 -1.0062621

1.3198246 -1.102322 3.3269203 -1.0040368

1.412318 -1.1017926 3.4287536 -1.0021176

. 1.5065128 -1.0986553 3.5303976 -1.000473

1.6022571 -1.0936868 3.6318546 -0.99907337

1.6993889 -1.0874984 3.7331303 -0.99789094

1.7977411 -1.0805681 3.8342327 -0.9969001

1.8971455 -1.0732652 3.9351713 -0.99607738

1.9974369 -1.0658709 4.0359568 -0.99540153

2.0984569 -1.0585944 4.1366007 -0.99485338

2.2000568 -1.0515868 4.2371146 -0.99441577

2.3021

-1.0449529

4.33751 -0.99407342

2.4044637 -1.0387603 4.4377982 -0.99381281

2.5070395 -1.0330478 4.5379902 -0.99362199

161

the method, we explored the possibility of making recourse to the

relationship between Sturmian orbitals and STO.

In practice, since Rico and collaborators have proposed, implemented and made available an ecient program for the calculation

of two-center monoelectronic integrals involving STO, based on the

recurrence relationships which they enjoy [29, 30], and since the

Sturmian orbitals can be given as simple linear combinations of the

STO (explicitly, indicating the latter as nlm :

u1;0;0

u2;0;0

u2;1;m

u3;0;0

u3;1;m

u3;2;m

u4;0;0

u4;1;m

u4;2;m

= 1;0;0 p

= 1;0;0

3 2;0;0

= 2;1;m p

p

= q

2;0;0 + 10 3;0;0

1;0;0 2 3 p

= 2 23 2;1;m

5 3;1;m

(5.19)

= 3;2;m p

p

p

= 1;0;0 3 3 q2;0;0 + 3 10 3;0;0

35 4;0;0

p

p

3

= 5 2;1;m p

5 2 3;1;m + 21 4;1;m

3

= p2 3;2;m

7 4;2;m

the bicenter monoelectronic integrals S and M. The W integrals

can instead be calculated analytically even though the exponents

dier.

However, this program doesn't calculate the three-center monoelectronic integrals

Z

dx unlm (x)

jx Xa j un0l0m0 (x Xa0 )

(5.20)

162

The most demanding eort for our valence-bond Sturmian approach appears, as usual in quantum chemistry, when the calculation of the bielectronic multicenter integrals is needed:

Z Z

0

0

jx x0 j u (x )u (x )

C

(5.21)

Our test cases presented in Sec.5.2.1 were tackled in a rather tortuous manner, making recourse to another program due to Rico

and coworkers [31] which in turn in order to obtain integrals for

STO expands them as linear combinations of GTO. The resulting

Gaussian integrals are nally calculated using available techniques.

The ensuing disadvantage of this inelegant procedure is that, since

a satisfactory t of an STO requires about 10 Gaussians, an integral involving four STO's requires the calculation of 104 integrals

among GTO. Moreover our integrals such as (5.21) are linear combinations of integrals among STO: for example an integral involving

four 3s-Sturmians requires a sum over 34 integrals of the STO program, and therefore 34 104 integrals over Gaussians. Therefore

this program, which recommends itself for the accuracy which can

be adjusted due to
exibility in the choice of the number Gaussians required to approximate a STO and satisfactorily covers the

range of permitted quantum numbers (nmax = 6; lmax = 3), although appropriate for test calculations, must be superseded by

more direct approaches to tackle integrals such as Eq.(5.21). Alternatives should also be explored, involving for example elliptic or

other suitable coordinates.

163

The account presented in this chapter on developments regarding

the use of Sturmians orbitals in quantum chemistry demonstrates

how fruitful was the idea put forward long ago by Shull and Lowdin

of "natural spin orbitals". The rst steps of the proposed approach

show perspectives of advantages over conventional methods, particularly for excited states. Not considered in this chapter have been

the alternatives which open by exploiting the various ways available

to separate variables for Eq.(4.1): they have been recently classied

both in conguration [21] and in momentum space [22]. Since the

computation of integrals is a feature which will eventually decide

the crucial potentialities and scope of the Sturmian approach, the

alternative basis sets and the relationships among them are an important goal to further study; some progress have been made for

the parabolic set [12, 13].

Needless to say, these orbitals might nd a specic role also

whenever in quantum chemistry there is a need for an expansion

in a complete basis set. Further extensions which are of relevance

for the application to heavier systems are those involving the inclusion of relativistic eects: see Chapter 8 in Ref. [10] and recent

work by Smitkowski [34{37]. For the particular scheme introduced

in Sec.(5.2.1) the numerical results on H2 indicate that the development of a direct algorithm for the calculation of bielectronic

multicenter integrals would greatly contribute to practical imple-

164

mentations to systems of increasing complexity. Our current eort

on this problem shows the importance of using momentum space

techniques, which allow the exploit of powerful angular and hyperangular momentum algebra.

centered on two dierent nuclei a and b, separated by a distance R:

b;n0 l0 m0

a;nlm

ua;n0l0m0 (x)ub;nlm(x)dx

(5.22)

Z

ipR

nlm (

p) n0l0m0 (p)dp

(5.23)

relationship between nlm (p) and hyperspherical harmonics (Eq.

2.4), and the volume element in p-space:

!

k2 + p2 3

d

dp =

2k

(5.24)

0 l0 m0

3=2

Mb;n

a;nlm = (2 )

Z

4 k 5= 2

d

2 2 2 Ynlm (

)Yn0 l0 m0 (

)Yn00 l00 m00 (

)

(p + k )

(5.25)

165

One can easily transform the fourth relationship in Eq.(2.3) into

(1 + cos )2 =

4k5=2 3=2

k

(k2 + p2 )2

(5.26)

!

2 3=2 X

=

un00 l00 m00 (x)

k

n00 l00 m00

b;n0 l0 m0

a;nlm

M

Z

(5.27)

d

(1 + 2 cos + cos2 )Ynlm (

)Yn0 l0 m0 (

)Yn00 l00 m00 (

)

as (Eq. 2.32 in Ref. [6]):

Ynlm (

)Yn0 l0 m0 (

) =

N;L;M

"

#

nn0 N (2l + 1)(2l0 + 1) 1=2

2 2

8 0

n

>

>

< 2

1

0

n 1

2

l0

n 1

2

n 1

(5.28)

N 1 >

=

2 >

N 1

Y

NLM

>

>

;

(

)

l

L

From a three-term recurrence relationship involving Gegenbauer

polynomials [38], we have obtained the following expression:

:

cos YNLM (

) =

v

u

u

t

1 (N L)(N + L + 1)

YN +1;LM (

) (5.29)

2

N (N + 1)

v

u

L 1)

1u

t (N + L)(N

YN 1;LM (

)

2

N (N 1)

Inserting Eqs.(5.28) and (5.29) into Eq.(5.27), we get a solution

for the integral:

b;n0 l0 m0

a;nlm

!

"

#

2 3=2 X nn0 N (2l + 1)(2l0 + 1) 1=2

=

k

2 2

NLM

(5.30)

166

8 0

> n

>

< 02

:

("

1+

l0

n 1

2

n 1

N 1 >

=

2 >

N 1

>

>

;

L)(N + L + 1) (N + L)(N L 1)

+

(1 N;1 )

4N (N + 1)

4N (N 1)

(N

v

u

u

t

uNLM (x)

v

u

u

t

v

u

4(N

(N

L)(N + L + 1)

uN +1;LM (x)

N (N + 1)

(N + L)(N L

N (N 1)

1 u

t (N

+

4(N + 1)

+

1

n 1

2

1)

v

u

u

t

1)

N (N + 2)

L2 ]

(N + L)(N

1)2

L 2)[(N

N (N 2)

uN +2;LM (x)

L2 ]

Bibliography

[1] H. Shull and P.-O. Lowdin,

[2] V. Fock,

J. Chem. Phys.

, 98,145 (1935).

Z. Phys.

Chemistry group, Uppsala University (1968).

[5] K.M. Howell and H. Shull,

J. Chem. Phys.

Academic Press, New York (1975).

.

167

[7] V. Aquilanti, , S. Cavalli, C. Coletti, D. Di Domenico, and

G. Grossi. Quantum Systems in Chemistry and Physics. Vol I:

Basic Problems and Model Systems, page 289 (2000).

[8] J. Avery, Hyperspherical Harmonics, Applications in Quantum

Theory. Kluwer Academic Publishers, Dordrecht, The Netherlands

(1989).

[9] T. Shibuya and C.E. Wulfman, Proc. Roy. Soc., A286, 376 (1965).

[10] J. Avery, Hyperspherical Harmonics and Generalized Sturmians.

Kluwer Academic Publishers, Dordrecht, The Netherlands (2000).

[11] J. Avery,

209, 405 (1996).

[13] V. Aquilanti, S. Cavalli, and C. Coletti,

(1997).

[14] J.P. Gazeau and A. Maquet,

[15] B.K. Novosadov

[16] Brett I. Dunlap

, 214, 1

Chem. Phys.

J. Chem. Phys.

Opt. Spectrosc.

Chem. Phys.

, 30, 39 (1975).

15, 1227 (1982).

J. Phys. A

Phys., 76, 445 (1982).

J. Chem.

[19] H.J. Monkhorst and B. Jeriorski, J. Chem. Phys., 71, 5268 (1979).

[20] V. Aquilanti and J. Avery,

92, 99, (2003).

, 267, 1 (1997).

,

168

[22] V. Aquilanti, A. Caligiana, S. Cavalli and C. Coletti, Int. J. Quantum Chem., 92, 212, (2003).

[23] P. M. Morse and H. Feshbach,

McGraw-Hill, New York (1953).

J. Chem. Phys.

J. Chem. Phys.

, 89, 983 (1988).

, 83, 1 (2001).

, 39, 71 (2001).

J. Chem. Phys.

(1988).

, 9, 790

J. Comp. Chem.

Commun., 64, 329 (1991).

[31] J.F. Rico, R. Lopez, I. Ema and G. Ramrez,

mun., 105, 216 (1997).

Comp. Phys.

Physics, Vol. 1, Kluwer Academic Publishers (1998).

[33] J. Avery,

[34] R. Szmytkowski,

J. Phys. B

[35] R. Szmytkowski,

J. Phys. A

[36] R. Szmytkowski,

Phys. Rev. A

[37] R. Szmytkowski,

J. Phys. B

and

(2002).

, 31, 4963, (1998).

, 65, 012503 (2001).

[38] M. Abramowitz and I.A. Stegun. Handbook of Mathematical Function. Dover, New York, 1964.

Chapter 6

Anharmonic frequencies and Berry

pseudorotation motion in PF5

Summary

We study the dynamics of PF5 , using a density functional potential energy surface. The full surface has twenty D3h minima

connected by thirty C4v transition states. We use the theory of the

molecular symmetry group to understand the tunnelling splittings

of the vibrational levels. We estimate a value for the splitting by

studying the motion between two equivalent minima. This splitting is very small for the ground vibrational state. Therefore we

then study the vibrations of PF5 in one of its minima, using normal

coordinates with anharmonic perturbation theory and variational

theory. Our predicted fundamental frequencies agree well with observation. Finally we use the theory of the Reaction Path Hamiltonian to study the interaction of the vibrational modes with a large

169

170

amplitude motion connecting two minima.

6.1 Introduction

In this chapter, we shall study the Berry pseudorotation [1] dynamics of PF5 . Phosphorus penta
ouride has twenty equivalent

D3h minima which are connected by thirty C4v transition states.

Firstly we shall look at the structure of the vibrational energy levels including the eects of the multiple tunnellings, using the theory of the molecular symmetry group. We shall estimate a value

for the splittings which turns out to be very small for the ground

state. Then we shall look at the dynamics in the region of one

minimum, generating a quartic normal coordinate potential energy

surface using density functional theory. We use both perturbation

theory and variational theory to predict fundamentals, overtones

and combination bands.

We draw attention to some earlier studies on PF5 . Tschumper,

Fermann and Schaefer report structures, thermochemistry and electron anity using a variety of density functionals [2]. Wasada and

Hirao have studied the minimum and the transition state of the

pseudorotation using ab initio quantum chemistry [3]. They report

a barrier which is estimated between 1480 cm 1 and 1770 cm 1 .

Breidung and Thiel have used SCF theory to calculate an anharmonic force eld for PF5 . This reference provides a careful analysis

of the existing experimental data. The level of agreement they

171

obtained for the fundamentals (with MP2 for the quadratic force

constants) is similar to the accuracy we shall obtain using density

functional theory.

frequencies

We use density functional theory (DFT) for all our calculations of

the potential energy surface, specically employing three dierent

functionals (B97-1, B3LYP and B3P91), with a TZ2P basis set.

Our experience is that these hybrid calculations give potential energy surfaces with good structural features. The calculations were

done using CADPAC6.5 [4].

We located the D3h minimum and the C4v transition state. Geometrical parameters (which are dened in Figure 1) and the energy

barrier are given in Table 6.1.

The three computations show excellent agreement with the electronic diraction values [5] for the two bond lengths of the minimum (within the experimental error). The transition state barrier is uniformly predicted to be 1280 12 cm 1 . This agrees

well with other computations in the literature (for example Daul et

al. have reported a B3LYP/6-311++G(3df,3pd) calculation which

gives 1300 cm 1 [6]), but it is at variance with the earlier calculations of Wasade and Hirao (who only used a DZP basis in their

correlated studies). In Tables 6.2 and 6.3 we give the harmonic

172

l eq

l eq

l ax

l pi

l ot

l ax

l eq

l ax

l ot

l eq

l ot

2

x

D 3h

l eq

4

4

y

l eq

l ot

l ax

3

C 4v

D 3h

equivalent D3h minima by a C4v transition state.

173

Table 6.1: DFT optimization of PF5 ground state and the Berry

pseudorotation saddle point. (a Ref. [5]).

lax (

A)

leq (A)

Transition state (C4v )

lpi (

A)

lot (A)

(C4v ) (deg.)

Barrier to interconversion

E (cm 1 )

Expt.a

1.579

1.535

1.580

1.535

1.575

1.531

1.535

1.579

102.4

1.535

1.580

102.4

1.531

1.575

102.4

1279

1292

1271

1.577 0.005

1.534 0.004

that the one imaginary frequency of the transition state has B1

symmetry, and inspection shows that it corresponds to motion towards the D3h structure. The barrier at 1280 cm 1 is quite high

and so we must expect any ground state tunnelling features to be

very small; however we now proceed to study them.

174

Table 6.2: Calculated harmonic frequencies (cm 1 ) at the D3h minimum, compared with observed fundamentals from a Ref. [22] and

references therein.

Mode (D3h ) B97-1 B3LYP B3P91 Expt.a

1 (A01 )

792

783

792

816

0

636

626

634

648

2 (A1 )

00

3 (A2 )

934

920

933

946.4

00

4 (A2 )

559

557

560

575

0

5 (E )

1001

988

1000 1025.7

0

511

509

511

533

6 (E )

0

7 (E )

157

156

157

174

00

496

493

496

512

8 (E )

Let us consider the topology of the ground state potential energy

surface of PF5 . In this 12-dimensional hypersurface there are

!

5

2 = 20

2

equivalent minima, each one corresponding to a trigonal bipyramid (D3h point group) structure diering from the others only

for the labeling scheme of the nuclei. The PF5 molecule can undergo large amplitude motions: a well-known concerted mechanism,

called Berry pseudorotation (BP) [1], involves the lowest energy

barrier [7{9] for interconversion of equivalent minima. Such a motion is shown in Fig. 2: the transition state for the BP has C4v

symmetry, during the motion C2v symmetry is conserved (Fig. 3),

175

Table 6.3: Calculated harmonic frequencies in cm 1 for the C4v

transition state.

Mode (C4v ) B97-1 B3LYP B3P91

1 (A1 )

993

981

994

784

775

783

2 (A1 )

501

498

503

3 (A1 )

4 (B1 )

630

618

628

5 (B1 )

113i

117i

114i

6 (B2 )

558

554

558

966

949

964

7 (E )

8 (E )

552

547

552

356

354

357

9 (E )

and one of the three equatorial bonds (we call it `pivot') will be

almost unaected by the BP. Since there are three possible choices

for the pivot, each minimum (D3h ) is connected to the three nearest

equivalent minima on the surface by three equivalent paths. Thus

we are dealing with a potential energy surface having 20 equivalent

D3h minima and (20 3)=2 = 30 equivalent C4v transition states

(TS) connecting them in pairs. In Fig. 3 we report the Balaban

graph corresponding to our surface [10]. In the literature there

are several isomorphic versions of this graph, and we have tried to

choose an easily readable one.

We can determine the splitting patterns, i.e. the number and

the degeneracy of the splitting levels, by group theoretical considerations. If we neglected the presence of multiple minima, we could

176

C3 S 3

v

v

v

v

C2

C2

C2

C2

C4

C2

D3h

trigonal bypiramid

C 2v

intermediate configuration

C 4v

transition state

177

12

5

34

45

4

2

1

35

13

25

23

15

5

14

3

2

24

4

24

14

5

15

23

25

13

35

1

2

45

34

3

12

molecule XY5 . The D3h isomers are labeled by the numbers of the two

axial ligands, putting rst the one from which the equatorial ligands are

seen in clockwise sequence. If the two numbers are in decreasing order,

we invert and oversign them; such an isomer is the enantiomer of the not

oversigned one. The pivot which allows the passage between two isomers

has the number that does not appear in the labels of the isomers.

178

label the vibrational wavefunctions according to the irreducible representations of the D3h group. But when we want to consider the

interactions among several equivalent structures, we have to exploit

the molecular symmetry (MS) group to predict the degeneracy of

splitting levels and to label them [11]. The complete nuclear permutation inversion (CNPI) group of PF5 has 240 elements, being

the product of the complete permutation group (5! elements) and

the inversion group (2 elements). The MS group is a subgroup of

the CNPI group, obtained from the latter after deleting all the unfeasible elements, i.e. all the elements that interconvert numbered

equilibrium forms of the molecule separated by an insuperable barrier in the potential energy surface. For our molecule there is no

unfeasible element in the CNPI group, so this coincides with the MS

group. Then in order to predict the splitting patterns we have to

obtain the correlation between the A01 irreducible representation of

the D3h group and the corresponding irreducible representations in

the CNPI group G240 of PF5 . This was achieved using a code written by D. J. Wales [12]. The result is that the twenty ground state

vibrational levels span 6 irreducible representations: 2 of them are

non-degenerate, 2 are 4-fold degenerate and 2 are 5-fold degenerate.

In order to provide a quantitative estimation of the tunnel splittings, we exploit an approximate method described by Wales [12,

13]. This approach is an analogue to the LCAO method for the

construction of molecular orbitals. If there are n distinguishable

versions of a given structure, then there are n degenerate wave

179

functions, each localized on one particular potential energy well,

for any given vibrational state of the molecule. When rearrangements occur only between these n distinguishable versions, we may

approximate the true wave function as a linear combination of localized wave functions. We then construct the secular equations. In

the case of PF5 , there is just one type of degenerate rearrangement

which links 20 versions of the same structure. All the diagonal elements of the Hamiltonian H^ are the same (), and the o-diagonal

elements of H^ are denoted by , the tunneling matrix element, if

the corresponding minima are directly linked by the rearrangement

(adjacent), and are set zero otherwise. Then the splitting levels

are the eigenvalues of a 20x20 matrix which in each row has 3 odiagonal elements equal to and 16 equal to zero. Diagonalization

yields the splitting pattern for the ground state of PF5 , and the result, represented in Fig. 4, is seen to be consistent with the group

theoretical predictions.

Next we have to provide a numerical (approximated) value for

. Let us consider the equation

!

1 d2

+ V (Q) Ei 'i = 0

2 dQ2

(6.1)

mass-weighted Cartesian coordinates of PF5 , and V (Q) is one of

the 30 equivalent reaction paths connecting two minima by a saddle

(see Fig. 5). Each point of the path has been calculated with the

following method: a) enforce C2v symmetry; b) enforce atoms 1

180

(1)

+3

(4)

+2

A1

(5)

D3h

(5)

(4)

(1)

(20)

240

Figure 6.4: The splitting pattern for the vibrational ground state of

PF5 , taking into account the multiple equivalent minima. The numbers

between parentheses indicate the degeneracy of levels.

181

and 5 to be on the yz plane, and atoms 2 and 4 to be on the xy

plane (referring to Fig. 1); c) x a value for ; d) optimize all the

other internal degrees of freedom (we use the functional B3P91 and

basis set TZ2P). Eq.(6.1) is solved numerically, and the dierence

between the two lowest-lying levels is used to evaluate (Fig. 5):

E

' 2

E1

= 0:06 cm 1

(6.2)

Our estimated value of is indeed very small, and in fact no splitting due to Berry pseudorotation has been detected experimentally. Takami and Kuze have studied the 3 fundamental and the

3 + 7 7 hot band using infrared absorption spectroscopy. They

state that they do not observe any splitting attributable to BP with

their 10 MHz resolution [14]. Of course our calculation gives only

a crudest estimate for the splitting.

However, we nd that there will be a substantial splitting for

the higher vibrational levels. Table 2 shows that the magnitude of

the frequency of vibration which corresponds to interconversion is

160 cm 1 , i.e. seven quanta, suce to reach the top of the barrier. Therefore if it were possible to create such a highly excited

vibration, then the eects of BP would be observable.

We have therefore conrmed that the eects of BP are negligible for

the lowest vibrations of PF5 . We now consider one of the minima

182

Energy (Eh)

-840.72

-840.73

C4v

E2

-840.74

D3h

-400

E1

-200

D3h

0

200

Q (a.u.)

Figure 6.5: A C2v reaction path connecting a D3h minimum and a C4v

due to the interaction of the two minima is qualitative. The numerical

values for the levels E1 and E2 are the two lowest eigenvalues of Eq.

(6.1).

400

183

in isolation, using the B3P91 functional and the TZ2P basis set

to determine the anharmonic force eld. We expand the potential

energy surface through quartic terms:

1 X

1X 2 1X

!i qi +

ijk qi qj qk +

qqq q

(6.3)

2 i

6 ijk

24 ijkl ijkl i j k l

In this standard notation !i are the harmonic wavenumbers, qi

are the dimensionless normal coordinates, and ijk , ijkl are the

third and fourth order force constants, respectively. If Eq. (6.3)

corresponds to a Taylor series, then we use this identication:

V =

@ 3 V

ijk =

@qi @qj @qk 0

(6.4)

@4V

ijkl =

(6.5)

@qi @qj @qk @ql 0

As usual the third and semi-diagonal fourth order (iijk ) force

constants were evaluated by nite dierence calculations from analytical second derivatives obtained at the equilibrium geometry

and at the geometries displaced from equilibrium along the normal

modes:

(2qi )

(6.6)

(qi )2

(6.7)

ijk =

iijk =

184

We have discussed elsewhere how the magnitude of the displacements are chosen, and subsequent averaging [15]. Essentially the

displacement was chosen to be 100 Eh over the equilibrium geometry.

To obtain the vibrations on this potential energy surface, we

may use either perturbation theory or variational theory. Secondorder perturbation calculations were carried out using the program

`SPECTRO' [16]. In a simplest form, SPECTRO obtains the energy levels of an asymmetric top i.e. it determines the anharmonic

constants xkl

E (v) =

1

1

1 X

!k (vk + ) + xkl (vk + )(vl + );

2 kl

2

2

(6.8)

Fermi type I resonances and Fermi type II resonances. When they

occur the divergent part is removed and a resulting 2x2 matrix

is diagonalized. (for more details see Ref. [16]). The asymmetric

top formulae can be used for PF5 , all that is necessary is to very

slightly change (+7 10 6 amu) the mass of an equatorial uorine

to lower the symmetry from D3h to C2v . Results of the application

of perturbation theory are in Table 6.4.

In this case Fermi resonances were not found to be signicant,

the largest resonance occurring for 5 and 1 + 7 and producing a

shift of 0.03 cm 1.

It is well known that the second order perturbation theory ap-

185

Table 6.4: Fundamental frequencies (cm 1 ) from a quartic force

eld (DFT B3P91/TZ2P, Eq. 6.3), calculated by b perturbation

theory (SPECTRO) and cvariational theory (MULTIMODE). a See

Ref. [22] and references therein.

Mode (D3h )

1 (A01 )

2 (A01 )

3 (A002 )

4 (A002 )

5 (E 0 )

6 (E 0 )

7 (E 0 )

8 (E 00 )

PTb

786

629

926

557

991

512

157

493

VTc a Expt.

787 816

630 648

927 946.4

557 575

992 1025.7

512 533

157 174

493 512

only for Morse potential. Therefore, this approach in eect \Morsies" the potential of Eq. (1). This can be viewed as replacing

the polynomial expansion in normal coordinates Qi by polynomial

expansion in the Morse coordinates yi = 1 exp( i Qi ) so that the

rst through fourth derivatives of potential with respect to Qi stay

the same. However, this introduces higher-order terms into the potential, which in many cases may bring the vibrational levels closer

to reality. To nd the true eigenvalues of Eq. (1) we use variational

theory. The variational normal coordinate code `MULTIMODE' is

based on the Watson representation for the kinetic energy operator [18]. It was rst used to perform vibrational self-consistent eld

186

(SCF) calculations, which were followed by conguration interaction (CI) using the orthonormal virtual expansion functions of the

SCF zero-point level. The `MULTIMODE' package has been described previously [19]. `MULTIMODE' uses numerical integration

for the matrix elements. We use the parameter Icoupl = 3 which

means that the code properly considers all terms in our potential

V . The Coriolis terms are evaluated up to the case when 3 normal

coordinates are simultaneously nonzero.

The SCF vibrational states are formed from a basis of NVF=6

optimised one-dimensional functions in the 12 normal modes. These

are in turn obtained from an initial set of 12 primitive harmonic oscillator basis functions, integrated over 15 points by Gauss-Hermite

quadrature, in matrix elements constructed from one-dimensional

cuts of the potential. For each required state the basis is diagonalised for each mode in turn in the eld of the remaining modes

in their respective states until self-consistency is reached.

For improved descriptions of the vibrational states we perform

CI. The CI basis is itself built from 1-mode, 2-mode, etc. expansion

sets in all normal modes of the molecule, i.e. from sets allowing

simultaneous excitation of one, two etc. modes. Each category is

subject to a maximum quantum Q for each mode and a maximum

sum S over all modes. We report calculations using four modes,

with Q=6 and S=6, in Table 6.4.

Table 4 shows a remarkable agreement between the perturbation

theory and the variation theory predictions for the fundamentals.

187

This is hardly surprising; when using the data from Table 2, it is

seen that the eects of anharmonicity are very small (less than 10

wavenumbers for each mode). The anharmonic eects are smaller

than the errors arising from the use of DFT, but even those do not

exceed 35 wavenumbers. Therefore the fundamentals of PF5 are

well reproduced by considering it as a rigid isolated molecule.

Hamiltonian

In the previous section the vibrations of PF5 were studied around

one of its minima, in complete isolation from its other minima.

At this particular minimum, there must be three large amplitude

motions which lead to the three transition states towards the three

neighbouring minima. The remaining motions can be described by

normal coordinates. Therefore for a complete study of PF5 we need

a representation with 9 normal modes and 3 large amplitude modes.

Such a mathematical formulation does not exist. However we have a

version of MULTIMODE which treats one large amplitude motion

using the theory of the Reaction Path Hamiltonian (RPH) [20].

We are presently developing a two large amplitude program, with

the Reaction Surface Hamiltonian [21] ; we can see how to treat the

extension to the Reaction Volume Hamiltonian, although a program

formulation is a long way o.

In this section we report studies using RPH. This requires the

188

determination of the `Reaction Path' connecting two adjacent minima (using DFT). Ideally we should nd the steepest descent path

from the TS to the minima (it is symmetric about the TS); for

simplicity we determined a closely related path which is parameterised by the angle (see g 1), enforcing C2v symmetry. The DFT

energy is minimised with respect to all other internal coordinates.

This gives the same reaction path as obtained in section 3. At each

point on the path (which is symmetric about the transition state),

the projected force constant matrix is determined, giving the harmonic frequencies and the associated vectors, which are required for

the RPH implementation. Our representation of the reaction path

through the angle allows an automatic continuation of it beyond

the minima by further reducing the angle . The greatest diculty

with the application of RPH is that the vibrational modes must

continuously change along the path, in particular at an accidental

crossing. This was carefully checked, and we also ensured that all

frequencies and vectors were symmetrical across the TS.

Eectively this entire calculation is an attempt to model the role

of the multiple minima on the vibrational dynamics. From section

3 we know the eects on vibrations along the paths connecting the

multiple minima, with levels at E0 ; E0 2; E0 3 . Here we

shall only obtain E0 . We therefore expect the zero point energy

to be split in this way, and indeed we expect all the vibrational

levels to be split, i.e. the number of levels will be doubled. Because

the reaction path motion is degenerate at the minima, we expect

189

the this motion to be split into 4, with two near pairs, corresponding

to motion along the path and motion perpendicular to the path. If

we were able to study the full problem then each original level E0

would be split into 6 levels, according to the theory of section 3.

We believe that the magnitude of the splittings should be in the

ratios given by section 3.

The results of the RPH calculations are given in Table 6.5.

The original MULTIMODE calculations are also given (as VT)

for comparison, in order to demonstrate the splittings discussed

above. The VT calculations use only the full quadratic force eld

at the minima (i.e. no anharmonicity); the RPH calculations use

only a quadratic force eld perpendicular to the path (i.e. only

anharmonicity along the path). The table shows the predicted levels for the zero point, the fundamentals, the overtone 27 and the

combination bands 7 + k (k=1-6,8). 7 corresponds to the (degenerate) motions at the minima, one of which corresponds to the

reaction path. All the expected splittings are present. Highlights

are

(i) the zero point motion is split by 0.13 cm 1 .

(ii) the degenerate mode 7 is split into two motions: (162.17,

162.54), which is perpendicular to the path (this is a fundamental vibration), and (195.75,197.40), which corresponds to the rst

excited vibration along the path, with a consequent larger splitting.

(iii) a nondegenerate fundamental, such as 1 is split (798.79,798.92)

by 0.13 cm 1 .

190

(iv) the combination 8 + 7 , both originally degenerate, now

correspond to 8 levels, easily identiable as 4 related pairs.

We therefore believe that these RPH calculations have gone

some way towards providing a numerical demonstration of the expected vibrational levels for PF5 .

6.6 Conclusion

In this chapter we have studied the dynamics corresponding to the

low lying vibrations of PF5 . We have used density functional theory

to determine the important aspects of the potential energy surface,

a theory which we believe is entirely adequate for these purposes,

bearing in mind that we do not study parts of the surface which

involve the breaking of bonds. We have calculated the barrier to

interconversion between equivalent minima to be 1280 cm 1 .

Firstly we studied the eects of tunnelling motion on the vibrations around the twenty minima which are connected by thirty

transition states. We used the Molecular Symmetry group to predict the degeneracies of the vibrations; we also used a Huckel type

analysis for this purpose. We predicted that the splittings of these

vibrations are very small.

Secondly we studied the anharmonic motion of PF5 around one

of its minima, using both perturbation theory and variational theory. We compared our predictions for the fundamentals with those

available in the literature, agreement to 15 cm 1 being obtained.

191

Finally we use the Reaction Path Hamiltonian to study the vibrations with one large amplitude motion connecting two adjacent

minima. We were able to interpret the resultant splittings of the vibrations and would also predict the nature of the vibrational levels

if it were possible to include the eect of all the minima simultaneously.

To sum up, the principal weakness of the work presented in this

chapter is the use of Density Functional Theory to generate the

potential energy surfaces. We were interested in a study of the dynamics, and methods for this, and we believe that our methods are

completely appropriate to a more accurate potential energy surface.

From the calculations of Wasada and Hirao [3] one possibility is that

our transition state is too low. However a much greater criticism

is that we have only been able to calculate the interactions of one

minima with another, and not the interactions of one with minima

with three other minima. The eect of including all the interactions simultaneously will be to substantially reduce the tunnelling

splitting, but at present we have no numerical way of determining

this, which should require that the large amplitude motion be occurring on at least a two-dimensional surface, to accomplish for the

trifurcation of the reaction path from each minimum towards its

neighbours.

192

Bibliography

[1] R. S. Berry,

J. Chem. Phys.

Phys., 104, 3676, 1996.

[3] H. Wasada, K. Hirao,

J. Chem.

[4] R.D. Amos, I.L. Alberts, J.S. Andrews, S.M. Colwell, N.C. Handy,

D. Jayatilaka, P.J. Knowles, R. Kobayashi, G.J. Laming, A.M. Lee,

P.E. Maslen, C.W. Murray, P. Palmieri, J.E. Rice, E.D. Simandiras,

A.J. Stone, M.-D. Su, and D.J. Tozer, Cadpac6.5, The Cambridge

Analytic Derivatives Package (University of Cambridge, UK), 2000.

[5] L. S. Bartell, K. W. Hansen,

, 4, 1775, 1965.

Inorg. Chem.

74, 1996.

[7] P. Russenger, J. Brickmann,

J. Chem. Phys.

J. Chem. Phys.

, 66, 1, 1977.

Press, New York, 1976.

[11] P. R. Bunker, Molecular

Press, New York, 1979.

[12] D. J. Wales,

[13] D. J. Wales,

, Academic

, 80, 2314, 1984.

J. Chem. Phys.

Chem. Phys., 112:248, 2000.

193

[16] J.F. Gaw, A. Willetts, W.H. Green, and N.C. Handy, in "Advances

in Molecular Vibrations and Collision Dynamics", ed. J.M. Bowman, JAI Press, Greenwich, CT (1990).

[17] D. Papousek, M.R. Aliev, Molecular Vibrational-Rotational Spectra, Academia, Prague (1982).

[18] J. K. G. Watson,

Mol. Phys.

100, 191, 1998.

[20] D. P. Tew, N. C. Handy and S. Carter Mol. Phys., 99, 393 (2001).

[21] D. P. Tew, N. C. Handy and S. Carter J. Chem. Phys., submitted

[22] J. Breidung, W. Thiel,

J. Mol. Struct.

194

Table 6.5: Fundamental frequencies, and overtones and combination bands involving 7 calculated with Multimode (VT) and the

reaction path Hamiltonian (RPH). Only harmonic terms are included in the normal coordinate forceeld

Mode (D3h )

VT

RPH

0

1 (A1 )

792

798.79,798.92

0

635

640.01,640.12

2 (A1 )

3 (A002 )

936

938.95,939.05

00

4 (A2 )

562

565.98,566.16

0

5 (E )

1001;1001

1004.15,1004.33;1006.40,1006.59

0

6 ( E )

515;516

505.54, 505.76;519.31,519.44

0

162;163

162.17,162.54;195.75,197.40

7 (E )

00

8 (E )

498;499

500.78,500.86;502.61,502.77

27

324;325;325

321.24,324.27;366.99,368.98;384.57,388.70

943

961.23,962.64;992.68,993.23

1 + 7

2 + 7

797;798

802.45,803.82;835.51,836.10

3 + 7

1098;1098

1101.37,1102.78;1135.71,1136.29

4 + 7

724;725

729.95,730.75;764.76,766.07

5 + 7

1163;1164;1164;1164

1167.43,1168.74;1199.76,1200.33

6 + 7

678;678;678;679

667.63,669.13;681.47,683.33;703.07,703.79;718.18,718.92

660;661;661;661

662.77,664.57;666.77,667.26;694.16,694.66;703.95,705.04

8 + 7

Contents

195

196

Conclusions

Here we summarize the main results exposed in this work. The

chapters of this thesis originated several publications that are listed

in the Bibliography of the present section.

In chapter 1 [1] we have studied the four dierent types of Sturmian orbitals arising from the separation of variables in Schrodinger

equation for the hydrogen atom: polar, parabolic, spheroidal and

spheroelliptic. The denition of spheroidal and spheroelliptic Sturmians includes a continuous parameter, which allow them to perform smooth transitions respectively from polar to parabolic Sturmians and from polar Sturmian oriented towards an axis to polar

Sturmian oriented towards a dierent axis. The symmetry properties of the alternative basis sets and the orthonormal transformations to each other have been investigated.

In chapter 2 [2] we have studied the corresponding problem for

Sturmians in momentum space (there are six types of them: spherical, Stark, Zeeman, spheroelliptic, elliptic cylindrical of type I and

II), exploiting in our investigation the method of trees and the

close relationship with hyperspherical harmonics. Then, we have

197

198

discussed the connections among basis sets in the conguration

and momentum space. Spherical, Stark and spheroelliptic Sturmians in momentum space are respectively the counterparts of polar,

parabolic and spheroelliptic Sturmians in conguration space. Elliptic cylindrical Sturmians of type I and II include a continuous

parameter that allows them smooth transitions between Stark and

Zeeman functions, and spherical and Zeeman functions respectively.

In chapter 3 we have applied one type of Sturmian orbitals in

conguration space (the polar ones) to the solution of Schrodinger

equation for atoms. The consequences arising from the use of Sturmians has been exposed: the kinetic energy operator disappears

from the secular equation; the representation of the nuclear attraction potential is diagonal; the eigenvalues are not the energies of the

p

2E ; since the orbitals are not orthogonal, matrix

system, but

elements are to be calculated in the framework of Slater-Condom

generalized rules; the eect of external elds could be easily incorporated in our formalism. A calculation on Helium atom electronic

states has shown that the description of excited states is very good

allowing one to simulate easily the atomic spectrum. This is at

variance with conventional quantum chemistry methods. An application of the method in the case of external eld has been performed

in order to compute the rst order static polarizabilities of Lithium.

Chapter 4 deals with Sturmians and one-electron molecules [3].

Analytical formulas were obtained for nuclear attraction integrals

involving polar and parabolic Sturmians. A calculation of the po-

199

tential energy curve of H+2 has been performed in order to test the

convergence properties of Sturmian basis sets at dierent levels of

iteration of the secular equation.

In chapter 5 [4, 5] we have proposed an original method for

solving the molecular Schrodinger equation for molecules, inserting

Sturmian orbitals into a valence bond approach. We have not been

able to solve analytically multicenter repulsion integrals involving

Sturmians, so we had to expand the latters as linear combinations

of Gaussian functions and solve numerically the integrals. We calculated the potential energy curve for H2 , demonstrating that such

a method can be practically implemented.

Chapter 6 [6] is not closely related to the previous ones. We

studied the dynamics of PF5 , using a density functional potential

energy surface. The full surface has twenty D3h minima connected

by thirty C4v transition states. We used the theory of the molecular

symmetry group to understand the tunnelling splittings of the vibrational levels. We estimated a value for the splitting by studying

the motion between two equivalent minima. This splitting is very

small for the ground vibrational state. Therefore we then studied

the vibrations of PF5 in one of its minima, using normal coordinates

with anharmonic perturbation theory and variational theory. Our

predicted fundamental frequencies agree well with observation. Finally we used the theory of the Reaction Path Hamiltonian to study

the interaction of the vibrational modes with a large amplitude motion connecting two minima.

200

Bibliography

[1] V. Aquilanti, A. Caligiana and S. Cavalli,

Chem., 92, 99, (2003).

Int. J. Quantum

Quantum Chem., 92, 212, (2003).

Int. J.

(2002).

submitted (2003).

Kryachko (Eds.), 2003 Kluwer Academic Publishers.

[6] A. Caligiana, V. Aquilanti, R. Burcl, N.C. Handy, D.P. Tew,

Chem. Phys. Lett., 369, 335, (2003).

- Istituzioni Di Fisica Nucleare - CeradiniIstituzioni Di Fisica Nucleare - CeradiniParide D'Ostilio
- appunti_teoricaappunti_teoricalinux14
- 7605-Cagnetta-specialistica7605-Cagnetta-specialisticaswazi725
- Davide Cieri - Studio della Vita media del mesone BDavide Cieri - Studio della Vita media del mesone BDavide Cieri
- Appunti di Fisica Superiore (Prof. P. Brovetto). L’Interazione elettromagnetica: Teoria classicaAppunti di Fisica Superiore (Prof. P. Brovetto). L’Interazione elettromagnetica: Teoria classicaPier Franco Nali
- Elettrotecnica - AppuntiElettrotecnica - AppuntiPino Spinetti
- Teoria della Relatività Speciale, Formulazione Matematica - MorettiTeoria della Relatività Speciale, Formulazione Matematica - Moretticesarantoine
- introduzione alla sismologia sperimentaleintroduzione alla sismologia sperimentaleddpros
- Fondamenti Di Elettrochimica - MussiniFondamenti Di Elettrochimica - Mussiniflex
- Energia nucleare - tesi di laureaEnergia nucleare - tesi di laureaFlorin Zachia
- Saggioro_ElenaSaggioro_ElenaJorge Faustino pineda carbajal
- Appunti Ummarino Fisica IIAppunti Ummarino Fisica IISimone Santia
- Simulazione_dinamica_del_moto_di_un_giroscopio.pdfSimulazione_dinamica_del_moto_di_un_giroscopio.pdfLeonardo Monaco
- Bassani Grassano - Fisica Dello Stato SolidoBassani Grassano - Fisica Dello Stato SolidoFabz90
- T_di_Gauge_mainT_di_Gauge_mainLeonardo Monaco
- Istituzioni Di Meccanica QuantisticaIstituzioni Di Meccanica Quantisticanp484
- mc13studmc13studFrancesco Montagnoli
- Rimozione di artefatti fisiologici negli studi di connettività funzionale del cervelloRimozione di artefatti fisiologici negli studi di connettività funzionale del cervellopaolobarucca
- FISICA (12CFU) Michelotti AA2012-13 DefinitivoFISICA (12CFU) Michelotti AA2012-13 DefinitivoDe Sire Dario
- Fisica Nucleare e SubnucleareFisica Nucleare e Subnuclearenicolafratianni
- programma_2017_2018 fisicaprogramma_2017_2018 fisicacostanza.guarn
- Vanzo Lecture NotesVanzo Lecture Notes