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Abstra
t. We des
ribe and extend our re
ent proposal to model mathemat-
i
ally the vibrational levels asso
iated with Hydrogen bonds in symmetri
tri-atomi
mole
ules. Our approa
h is based on modi
ation of the usual
Born-Oppenheimer approximation to take into a
ount the lighter mass of the
Hydrogen nu
leus and the weakness of the Hydrogen bond, using spe
ial fea-
tures of the ele
tron energy level surfa
e asso
iated with the Hydrogen bond.
Negle
ting bending of the mole
ule for simpli
ity, we a
hieve this by s
aling
the mass of the Hydrogen atoms dierently from the heavier atoms, and by
using a modied form for the ele
troni
energy surfa
e.
As a result, anharmoni
ee
ts play a role at leading order in the limit
where the nu
lear masses go to innity. Our analysis is based on
lose exam-
ination of the numeri
al data available for the ground state energy surfa
e of
the F HF ion, and we make a
omparison with experimental data for the
vibrational levels of that ion.
The theory we propose is, however, quite general and
an a
omodate
asymmetri
tri-atomi
mole
ules. Moreover, we provide an extension of our
results to mole
ules with nu
lei of several dierent spe
ies, where we assume
that ea
h of the masses s
ales dierently. Considering an adapted ground
state energy surfa
e, we
ompute the leading term of the
orresponding vibra-
tional levels in the limit of large nu
lear masses by means of a normal form
Hamiltonian.
1. Introdu tion
More pre
isely,
onsider a mole
ular system whose nu
lear
onguration spa
e
modulo rotations is Rd , and denote the ratio of mean of the nu
lear masses to the
ele
tron mass be . For small , there exists a mole
ular energy level E () that
4
satises,
(1.1) E () = E + (n + 12 ) ! + (nd + 21 ) !d + O( );
0
2
1 1
4
where E is the minimum of the ground state ele
troni
energy level. The numbers
0
nj 2 N , and !j > 0, for j = 1; ; d,
hara
terize the d-dimensional harmoni
os
illator. Under quite general hypotheses, (1.1) represents the rst few terms in a
omplete asymptoti
expansion of E () in powers of . See the re
ent review [ ℄ for
4
more details and results.
For many mole
ules, this approximation is very su
essful, but it may fail to
give a
urate results when applied to some mole
ules that
ontain Hydrogen bonds.
The binding energy of Hydrogen bonds is typi
ally very small, and the mass of the
Hydrogen nu
leus is an order of magnitude smaller than that of other nu
lei su
h
as Carbon. Moreover, the experimental vibrational spe
tra of symmetri
tri-atomi
mole
ules with Hydrogen bonds display signi
ant deviations from the approximate
harmoni
spe
trum (1.1). See [ ℄ for an a
ount of these properties.
2
In [ ℄ we propose an alternative to the Born{Oppenheimer approximation that
3
is spe
i
ally designed to des
ribe mole
ules with symmetri
al Hydrogen bonds.
There are two main dieren
es between our approa
h and the standard Born-
Oppenheimer analysis. First, we s
ale the masses of the Hydrogen nu
lei as 3
while keeping the heavier nu
lei s
ale as . Although our analysis applies only
4
taking the mass of a Carbon atom to be . This value of is roughly ' 0:082.
4
Se
ond, we model the ele
tron energy level surfa
e in a spe
ial way that depends on
. This takes into a
ount the smallness of a
oeÆ
ient in the harmoni
potential
asso
iated with the Hydrogen bond. That
oeÆ
ient is weaker than the others,
roughly by a fa
tor . Consequently, in our model, anharmoni
ee
ts
ontribute
to the leading order
al
ulations of vibrational levels, as ! 0.
Our approa
h gives rise to an {independent normal form Hamiltonian HNF
(des
ribed below) whi
h is not a harmoni
os
illator. This Hamiltonian des
ribes
the vibrational levels: For small , there exists a mole
ular level E () that satises
(1.2) E () = E + E + O( );
0
2
2
2+
for some > 0, where E is an element of the spe
trum of HNF . Note that the
2
index 2 refers here to the power of appearing as the leading term. Again, under
appropriate hypotheses, our analysis yields a
omplete expansion of E () in powers
of = .
1 2
nu
lei and the Hydrogen nu
lei involved in the symmetri
Hydrogen bonding are
of order . Furthermore, anharmoni
ee
ts must be taken into a
ount for a
2
are harmoni
at that order. Anharmoni
orre
tions rst enter at order . 4
HYDROGEN BONDS AND SEMICLASSICAL NORMAL FORMS 3
We
onsider a mole
ule that
onsists of two types of atoms. Two identi
al
nu
lei are heavier and have masses , where the mass of an ele
tron is 1. The
4
third nu
leus is lighter and has mass . We
onsider a simplied model in whi
h
3
bending and rotational motions are absent, i.e., all three nu
lei lie on a xed line.
After passing to Ja
obi
oordinates, dis
arding kineti
energy of the
enter of mass,
and res
aling by
onstant numeri
al fa
tors (See [ ℄), the mole
ular Hamiltonian
3
has the form,
4
3
Hmol () =
2 x1 2 x2 + h(x ; x );
2 2
1 2
where x denotes the distan
e between the two identi
al nu
lei, and x is the
1 2
dispa
ement of the lighter nu
leus from the
enter of mass of the identi
al nu
lei.
Further te
hni
al hypotheses are provided below in Assumption 3.1.
The ele
troni
Hamiltonian h(x ; x ) depends parametri
ally on the positions
1 2
of the nu
lei. It is a self-adjoint operator on the ele
troni
Hilbert spa
e Hel . We
4 GEORGE A. HAGEDORN AND ALAIN JOYE
here, the equilibrium position of the lighter nu
leus lies at the
enter of mass of the
heavy nu
lei (xeq = 0). The non-symmetri
al
ase would have xeq 6= 0.
Thus far, we have only altered the standard Born-Oppenheimer approximation
2 2
by introdu
ing two nu
lear mass s
ales, instead of one. We now make a se
ond
modi
ation to re
e
t the stru
ture of the ele
tron energy level surfa
e asso
iated
with Hydrogen bonding. (See [ ℄.) We introdu
e an arti
ial dependen
e eqin the
2
ground state ele
troni
surfa
e on . After a shift of the variable x by x , we 1
assume that the ground state has an expansion of the form
1
oeÆ
ent makes it ne
essary to
onsider terms of order higher than quadrati
in the
2
expansion. We assume that a ; a and a are positive, but a
an take any eqvalue.
1 3 4 2
When a is negative, E (; x ; x ) has a
losely spa
ed double well near (x ; 0),
2 1 2
instead of a single lo
al minimum. Note that a = 0 leads to two de
oupled one-
1
3
dimensional systems, to leading order. We dene then a s
alar normal form by
keeping the leading order terms only in (2.1),
(2.2) 2 x1 2 x1 + E + a x + a x a x x + a x :
4 3
2 2 2 2 2 4
0 1 1 2 2 3 1 2 4 2
The S
hrodinger operator (2.2) plays the r^ole the Harmoni
os
illator plays in
the standard Born-Oppenheimer approximation. By res
aling with (y ; y ) = 1 2
(x =; x = = ), we see that (2.2) minus the
onstant term E is unitarily equivalent
1 2
1 2
0
to times the normal form Hamiltonian HNF ,
2
(2.3) HNF =
1 1
2 y1 2 y2 + ENF (y ; y )
2 2
1 2
with
ENF (y ; y ) = a y + a y 1 a y y +a y:
2 1
2
1 2
2
2 3 1
2
2 4
4
2
We further assume that the
oeÆ
ents faj g are su
h that the normal form potential
ENF is bounded below. More pre
isely, we require
2.1
Assumption .
a ; a ; a > 0; 1 3 4
and either
a < 4a a ; 2
3 1 4
or
a = 4 a a and a 0: 2
3 1 4 2
HYDROGEN BONDS AND SEMICLASSICAL NORMAL FORMS 5
Anti
ipating the result of the analysis below, the normal form HNF (2.3) yields
the leading term asymptoti
s (1.2) for the vibrational levels.
The spe
ial form (2.1) is motivated by numeri
al data for the mole
ule F HF .
By tting numeri
al data for F HF with the value = 0:0821, we get the following
quantities, where distan
es are expressed in Angstroms and energies in Hartrees.
xeq = 2:287; E = 200:215;
1 0
Note that the sum of the rst two eigenvalues is signi
antly larger than the third
one. This is an expression of anharmoni
ity.
By
omparison, if we use the data (2.4) in HNF , and numeri
ally determine
the vibrational levels using the rst two terms of (1.2) with = 0:0821, i.e.
E () ' E + E ; with E 2 (HNF );
0
2
2 2
our model predi
ts the following values for these vibrational modes:
600
m ; 1399
m ; and 1942
m :
1 1 1
Besides the relatively good agreement with the the experimental data, we also
point out that the anharmoni
ee
t mentioned above is present in our leading
term
omputation.
Standard Born{Oppenheimer based software yields
orresponding harmoni
modes
609
m ; 1118
m ; and 1727
m :
1 1 1
n
X j
(3.1) Hmol () = 2 x2j + h(; x); 1 2 n > 0:
j =1
6 GEORGE A. HAGEDORN AND ALAIN JOYE
Here, x 2 Rn , and Hel is the ele
troni
Hilbert spa
e. The ele
tron Hamiltonian
h(; x) is self-adjoint on an x{independent dense domain D Hel . We assume
h(; x) is bounded below, uniformly for x 2 Rn . Moreover, h(; x) is C 1 in the
strong resolvent sense and admits a non-degenerate {dependent ground state eigen-
value V (; x) with
orresponding normalized eigenstate (x), independent of . We
normalize the ground state energy surfa
e so that
(3.2) V (; 0) = 0:
We denote the formal Taylor expansion of V (; x) by
X
V (; x) v () x ; = ( ; ; n ) 2 N n ;
1 v () 2 R;
6 2Nn
0=
where the
oeÆ
ients v () are regular as ! 0. We impose more restri
tions on
these
oeÆ
ients below.
The rst step in analyzing the spe
trum of (3.1)
onsists of dening a s
alar
normal form Hamiltonian HNF . Let 2 (R )n be a set of positive exponents.
+
We
onsider the kineti
energy and introdu
e res
aled variables (y ; ; yn) = 1
(x =1 ; ; xn=n ), whi
h we denote by y = x=.
1
n
X j
2 x2j =
2 y ; for some > 0:
j =1
This enfor
es the relations
(3.3) j 2 j = ; 8 j = 1; ; n:
To determine the normal form potential VNF , we
onsider the formal expression
X
(3.4) V (; y) v () ( = ) jj y ; 1 2 ( +2)
6 2Nn
0=
of (3.4), and we want therep to be only nitely may su
h terms. All other terms
should
ontain fa
tors of with p positive. To make this more pre
ise, we make
the following assumption:
Assumption3.2 There exist > 0 and two non-empty nite sets of multi-
.
indi
es, Nn n f0g and F Nn n , su
h that for small jxj and ,
0 0
X X
(3.5) V
(; x) v ()
x
x
2 0 2 F
for some
> 0. Furthermore,
8
< v () ( = ) j j
1 2 ( +2)
=
; 8 2 0
(3.6) :
(j j + 2) > 0; 8 2 F :
3.3 We address the question of existen
e of a suitable and the
Remark .
orresponding sets and F for a given general potential at the end of this se
tion.
0
HYDROGEN BONDS AND SEMICLASSICAL NORMAL FORMS 7
Remark 3.4 The
ase of the tri-atomi
mole
ule in R is
hara
terized by the
.
2
sume that there exists a non-zero term of the form x00 in (3.4) with an -
independent
oeÆ
ient. Note, however, that it is possible to prove results similar
to the following one in
ase this hypothesis does not hold.
The next proposition gives
onditions on the {dependen
e of the
oeÆ
ients
v () (with 62 N ), ensuring that Assumption 3.2 holds, with an exponent
dened by means of the indi
es of the {independent non-zero
oe
ients of (3.4).
8 GEORGE A. HAGEDORN AND ALAIN JOYE
= min
2N 2 + j j
< n ;
0= f 2 Nn : (2 + jj) 0 g; and
F = f 2 N n n : j j < F g 0
The rst
on
ern is the spe
trum of the normal form Hamiltonian. We want
purely dis
rete spe
trum, whi
h is not obvious with our polynomial potentials V
that may or may not be
onning. Depending on the parameters, the set V (f0g) 1
may be unbounded. In order to ex
lude essential spe
trum, we
ould use Persson's
Theorem, as we did in [ ℄ for the tri-atomi
ase. A more general
riterion for the
3
absen
e of essential spe
trum for S
hrodinger operators with polynomial potentials
an be found in [ ℄ . Within our framework, it states the following:
7
1
For a polynomial V 0, dene X
(4.1) mV (x) = 1 + jD V (x)j;
2Nn
where D = x11 x22 . Note that the sum is nite.
xnn
Proposition 4.2 ([ ℄, Thm (1.3)) Let H satisfy Assumption 4.1 and let mV
7 .
be dened by (4.1). Then, the resolvent of H is
ompa
t if and only if
lim mV (x) = 1:jxj!1
Remark 4.3 The proof of this result in [ ℄ nds its roots in earlier work on
. 7
hypoellipti
operators. See e.g. [ ℄. 5
The fun
tion mNF
orresponding to the normal form Hamiltonian for tri-atomi
mole
ules, i.e., to the potential E (x ;x ) given by NF 1 2
(4.2) E (x ; x ) = a x + a
NF 1 2 a x x + a x;
1
2
1 2 3 1
2
2 4
4
2
is easily seen to tend to innity as jxj tends to innity if Assumption 2.1 holds
Hen
e, (HNF ) is dis
rete, for all allowed values of the parameters faj g.
For the general normal form potential VNF (3.7), we assume that the
orre-
sponding fun
tion mNF diverges at innity.
We also need to know that the eigenfun
tions de
ay exponentially, in a L 2
sense, together with their derivatives. This is the
ontent of the next result whi
h
is proven in [ ℄.3
Proposition 4.4 Let H satisfy Assumption 4.1, and assume that the spe
-
.
trum of H is dis
rete. Then, any eigenfun
tion x 7! '(x) 2 L (Rn ) is C 1 and, 2
q
(4.3) kp = rf k C kp = f k + kp = f k kp = f k + C kp = f k :
1 2 1 2 1 2 1 2 2 1 2 2
Remark 4.6 While Proposition 4.4 is suÆ
ient to derive the leading
ontri-
.
bution (1.2) of the vibrational spe
trum, the derivation of a
omplete asymptoti
expansion in powers of = requires a generalization to arbitrary derivatives of the
1 2
eigenfun
tion:
10 GEORGE A. HAGEDORN AND ALAIN JOYE
Proposition 4.7. Let H satisfy Assumption 4.1 and have dis
rete spe
trum.
Then any eigenfun
tion x 7! '(x) 2 L2 (Rn ) is C 1 and, for any a > 0, and any
multi-index
2 N n , D
' 2 D(eahxi ).
This result is proved by indu
tion on the order of
. The initial step is provided
by Proposition 4.4. The indu
tion step involves Paley{Wiener arguments. See [ ℄. 3
In this last se
tion, we show how leading order results of the type (1.2), or more
generally, of the type (3.8)
an be obtained by means of rather expli
it quasimodes.
The following theorem is the main result of this note. It is the generalization of
Theorem 3.6 in [ ℄ to the situation des
ribed in Se
tion 3.
3
Theorem 5.1 Let H () be dened by (3.1) and satisfy Assumption 3.1.
.
Assume the ground state V (; x) satises Assumption 3.2, and let HNF be the
mol
Then, for small , there exists an element E () of the spe
trum of H () that
mol
satises
E () = E + O( ): +
where F () 2 C (R; [0; 1℄) is even, supported on [ 2; 2℄, and equal to 1 on [ 1; 1℄.
1
We introdu
e a set of exponents (Æ ; ; Æn) with
1
whose values will be determined in the
ourse of the proof. We also use the short-
hand notation x=Æ = (x =Æ1 ; ; xn =Æn ).
1
Our quasimode is then dened as
(5.4) Q(; x) = (x) f (x=)F (x=Æ );
where (x) 2 Hel is the normalized ele
troni
eigenve
tor
orresponding to V (; x).
Consider its norm,
Z Z
(5.5) k Q()k = n jf (x=)j dx
2 2
n
(1 F (x=Æ )) jf (x= )j dx:
2 2
R R
The rst term is equal to jj by s
aling. Using the exponential de
ay of f , Propo-
sition 4.4, and the
onstraint (5.3) on the exponents, we see that the negative of
the se
ond term is bounded above by
Z
j j
Z P P
a nj=1 jyj j e a nj=1 jyj j jf (y )j dy
Æj
j f (x= )j dx
2
Æj j
e 2 2 2
(5.6) = O(1 ):
Altogether, this shows that k Q(; x)k = jj= (1 + O(1 )). Thus, to prove the
2
for some > 0. Using (3.1) and the denitions (3.7), (5.1), we see that
Hmol () Q () E Q () = (V (; x) VNF (x= )) Q (; x)
(5.8) R(; x);
where
n
X
R(; x) = j (x) f (x= ) x2j F (x=Æ )=2
j =1
X n
+ j xj ((x) f (x= )) xj F (x=Æ )
j =1
n
X
(5.9) + j f (x= ) x2j (x)=2 + xj f (x=) xj (x) F (x=Æ ):
j =1
We
onsider the rst two terms in R(), where and its derivatives are uniformly
bounded in a neigborhood of the origin. Be
ause of the derivatives of the
uto
fun
tion, there is always one dire
tion in whi
h the integration range is away from
the origin. Using this together with the fa
t that f and yj f are exponentially
de
aying in any dire
tion, an argument similar to that used in (5.6) shows that
these
ontributions
Pn
are O(1). The last
ontribution to R() is simply estimated
by O( j j j ), where jj=
omes from s
aling. By (3.3), j j =
j
=1
j =
2 2
+ j > , so that R() satises the bound (5.7). To bound the norm of the rst
12 GEORGE A. HAGEDORN AND ALAIN JOYE
2F jxj j2Æj
(5.10) ~ jj= Æ ; 2
to j , we get
2
jj= Æ = jj= Æ jj= ;
2 2+
with > 0;
2+
for suitable values of Æ and Æ , and where f is an eigenfun
tion of the normal form
1 2
(2.3). This shows that the amplitude of the distan
e between the two heavy nu
lei
is of order , whereas the Hydrogen atom
an move a larger distan
e away form its
equilibrium position, i.e., of order p.
Referen
es
[1℄ M. Born and J. R. Oppenheimer, Zur Quantentheorie der Molekeln. Ann. Phys. (Leipzig) 84
(1927), 457{484.
[2℄ N. Elghobashi, Theory of using few
y
les IR and UV laser pulses to
ontrol the orientation
and sele
tive disso
iation of Hydrogen-bonded anions, Ph D dissertation, Freie Universitat
Berlin, (2005).
[3℄ G.A. Hagedorn, A. Joye, A Mathemati
al Theory for Vibrational Levels Asso
iated with Hy-
drogen Bonds I: The Symmetri
Case, Preprint (2006).
[4℄ G.A. Hagedorn, A. Joye, Mathemati
al Analysis of Born-Oppenheimer Approximations, Pro-
eedings of the Conferen
e, \Spe
tral Theory and Mathemati
al Physi
s" in Honor of Barry
Simon, Mar
h 27{31 2006, AMS Pro
. of Symposia in Pure Math. (to appear).
[5℄ B. Heler, J. Nourrigat, Hypoellipti
ite maximale pour des operateurs polyn^omes de
hamps
de ve
teurs, Birkhaser, Boston, 1985.
[6℄ P. Hislop, Exponential de
ay of two-body eigenfun
tions: A review in \Mathemati
al Physi
s
and Quantum Field Theory", Henry War
hall (Editor), Ele
troni
J. Di. Eqns., Conf. 04
(2000), 265{288.
[7℄ A. Mohamed, J. Nourrigat, En
adrement du N() pour un operateur de S
hrodinger ave
un
hamp magnetique et un potentiel ele
trique, J. Math. Pures Appl. 70 (1990), 87{99.
Department of Mathemati
s and Center for Statisti
al Me
hani
s and Mathemati-
al Physi
s, Virginia Polyte
hni
Institute and State University, Bla
ksburg, Virginia
24061{0123, U.S.A.
E-mail address : hagedorn
alvin.math.vt.edu
Institut Fourier, Universite de Grenoble I, BP 74, F{38402 Saint Martin d'Heres
Cedex, Fran
e, and, Laboratoire de Physique et Modelisation des Milieux Condenses,
Universite de Grenoble I, BP 166, F{38042 Grenoble, Fran
e
E-mail address : alain.joyeujf-grenoble.fr