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PHYSICAL REVIEW A 73, 014501 2006

Generalized Thomas-Reiche-Kuhn sum rule


1

Bing-Lu Zhou,1 Jiong-Ming Zhu,1 and Zong-Chao Yan1,2

Department of Physics, Shanghai Teachers University, 100 Guilin Road, Shanghai, Peoples Republic of China 200234 2 Department of Physics, University of New Brunswick, Fredericton, New Brunswick, E3B 5A3, Canada Received 29 August 2005; published 24 January 2006 The generalized Thomas-Reiche-Kuhn sum rule is established for any Coulombic system with arbitrary masses and charges of its constituent particles. Numerical examples are given for the hydrogen molecular ions. DOI: 10.1103/PhysRevA.73.014501 PACS number s : 32.70.Cs, 32.10.Dk

I. INTRODUCTION

Polarizability of an atom or molecule is an important physical parameter that is a measure of response of a system to an external electric eld. The 2l-pole polarizability is dened in terms of a sum over a complete set of intermediate states, including the continuum 1 :
l

of electrons see Eq. 8 later . Both Eqs. 3 and 4 , however, cannot be applied directly to a molecular system. Our purpose in this Brief Report is to further extend the TRK sum rule to a system with arbitrary masses and charges of its constituent particles.
II. HAMILTONIAN

=
n 0

l f n0 , En E0 2 l f n0

1 is

where the 2l-pole oscillator strength


l l f n0 = f n0 m,M 0,M n =

In this work, atomic units are used throughout. Consider a Coulombic system of n + 1 charged particles. The nonrelativistic Hamiltonian is
n

8 En E0 2l + 1
n 2

H=
i=0

0 i

qiRliY lm Ri

1 2mi

n 2 Ri

+
i j 0

q iq j , Ri R j

In the above, the position vectors Ri are relative to the origin of a laboratory frame, qi is the charge of particle i, 0 is the wave function for the state of interest with the associated energy eigenvalue E0 and the magnetic quantum number M 0, and n is the wave function for one of the intermediate states with the associated energy eigenvalue En and the magnetic quantum number M n. A computationally feasible approach to obtain the spectrum n is to diagonalize the Hamiltonian of the system in a nite basis set. The quality of thus calculated polarizability depends on the degree of completeness of the spectrum. A useful method of judging the completeness is to check various sum rules. The most commonly used one is the Thomas-Reiche-Kuhn sum rule TRK , which states that for an atomic system of innite nuclear mass, the exact dipole oscillator-strength spectrum satises the following identity:
1 f n0 0,M 0,M n = Ne , n

where qi and mi are the charge and mass of the ith particle, respectively, and Ri is its position vector in a laboratory frame. The translational degrees of freedom can be eliminated by introducing the following transformation: r i = R i R 0, i = 1,2,3, . . . ,n,
n

1 m jR j , X= M T j=0

n where M T = i=0mi is the total mass of the system and X is the position vector for the center of mass relative to the laboratory frame. For a one-center atomic system, the nucleus is usually labeled as particle 0. Under this transformation, the transformed Hamiltonian becomes n

H=
i=1

1 2 i

2 i

1 m0 i

n i j 1 j + q0

n i=1

qi + ri i

n j 1

q iq j , rij 8

where Ne is the total number of electrons. Yan and Drake 2 extended the above TRK sum rule to the case of nite nuclear mass and obtained the modied expression
1 f n0 0,M 0,M n = Ne 1 + Neme/m0 , n

where rij = ri r j and i = mim0 / mi + m0 is the reduced mass between particles i and 0. In the above, the term 2 1 / 2M T X was neglected. This is because the transformed Hamiltonian does not contain X; thus X is a cyclic coordinate. The transformed Hamiltonian contains only the internal coordinates of the system.
III. THE GENERALIZED TRK SUM RULE

where me / m0 is the electron to nucleus mass ratio. It should be pointed out that 4 is not a simple scaling of 3 ; this is because for the nite nuclear mass case, the Hamiltonian contains the mass polarization terms and the reduced masses
1050-2947/2006/73 1 /014501 3 /$23.00 014501-1

The dipole operator in length gauge is


2006 The American Physical Society

BRIEF REPORTS
n

PHYSICAL REVIEW A 73, 014501 2006 TABLE I. Convergence of the sum over oscillator strengths for the ground state of H+. N denotes the size of basis set for the 2 2 intermediate states, SL = 2/3 d0 , and SR 2 2 2 = i=0 qi / mi QT / M T. N 448 575 725 900 1102 1333 1595 SR SL 1.000 835 680 1.000 820 799 1.000 817 725 1.000 817 129 1.000 817 025 1.000 817 005 1.000 817 000 1.000 816 999

d0 =
i=0

q iR i .

Using the new coordinates ri , d0 can be recast into in the center of mass frame
n

d0 =
i=1

ir i ,

10

where
i

= qi QT

mi , MT

11

n and QT = i=0qi is the total charge of the system. It is noted that for a neutral system where QT = 0, or for a system where mi / M T can be considered negligibly small, i = qi, as expected. One can similarly dene the dipole operator in velocity gauge as n

2 3

d0

=
i=0

2 q2 QT i , mi M T

20

b0 =
i=1

ip i ,

12

in length gauge. The parallel expression in velocity gauge is 2


n

where q0 qi . i= m0 mi Using the identity


i j,rs = js i+ is j,

3 13

b0

=
i=0

2 q2 QT i . mi M T

21

In fact, it is easy to see that 14 2 3 d0


2

2 3

b0

22

one arrives at the commutator relation: H,d0 = ib0 . Similarly,


n

15

d0,b0 = 3i
j=1

j j,

16

with the understanding that a , b = a b b a. Sandwiching and of the Hamiltonian Eq. 15 by two eigenstates H yields i d0 = b0 , 17

= E E is the transition energy. Furthermore, where d0 , b0 . Using Eq. 16 and inserting a comconsider plete set of energy eigenstates between d0 and b0, one obtains the following expression: 2 3
n

which establishes the equivalence between the length and velocity gauges of the oscillator strength. One can verify that, for an atomic system, the generalized Thomas-ReicheKuhn sum rule reduces to the original one 3 for the case of innite nuclear mass, as well as to its extension 4 by Yan and Drake 2 for the case of nite nuclear mass. As a numerical example, consider the ground state of H+ with the 2 proton mass taken to be 1836.152 701me. The wave functions for the ground state and the excited intermediate states of P symmetry, where P denotes the total angular momentum of the system, are constructed variationally using Hylleraas coordinates 3 . Table I shows a convergence of the sum over oscillator strengths, i.e., the left-hand side of Eq. 20 , as the size of basis set for the intermediate states increases progressively. In the table, the size of the ground state wave function is xed at 1330. One can see that the generalized TRK sum rule is clearly established numerically. Similarly, for HD+ with the deuteron mass of 3670.483 014me, the corresponding values are 2 3 and d0
2

d0

=
i=1

i i,

18

= 1.000 635 496

23

with the help of Eq. 17 . Since


n i i=1

Q2 = T i MT

n i=0

q2 i , mi

19

2 i=0

we nally obtain the generalized Thomas-Reiche-Kuhn sum rule

2 q2 QT i = 1.000 635 494, mi M T

24

respectively, which are in perfect agreement.

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BRIEF REPORTS IV. SUMMARY

PHYSICAL REVIEW A 73, 014501 2006 ACKNOWLEDGMENTS

In summary, the generalized TRK sum rule for dipole oscillator strengths has been derived for an arbitrary atomic or molecular system. It would be interesting to establish sum rules for any 2l-pole oscillator-strength spectrum with l 1. This has been done only for an atomic system with innite nuclear mass 4 .

Research support by the Natural Sciences and Engineering Research Council of Canada, by the Shanghai Municipal Education Commission No. O4DB16 , by ACRL, by SHARC-net, and by Westgrid is gratefully acknowledged. This work was also supported by the National Science Foundation through a grant for the Institute for Theoretical Atomic, Molecular and Optical Physics at Harvard University and Smithsonian Astrophysical Observatory.

1 Z.-C. Yan, J. F. Babb, A. Dalgarno, and G. W. F. Drake, Phys. Rev. A 54, 2824 1996 . 2 Z.-C. Yan and G. W. F. Drake, Phys. Rev. A 52, R4316 1995 . 3 Z.-C. Yan, J.-Y. Zhang, and Y. Li, Phys. Rev. A 67, 062504

2003 . 4 Z.-C. Yan, J.-M. Zhu, and B.-L. Zhou, Phys. Rev. A 62, 034501 2000 .

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