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**Semi
lassi
al Hamiltonian Normal Forms
**

George A. Hagedorn and Alain Joye

**Dedi
ated to Jean-Mi
hel Combes, in
elebration of his 65th birthday
**

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 features 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 examination 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 vibrational levels in the limit of large nu
lear masses by means of a normal form

Hamiltonian.

1. Introdu tion

The standard time{independent Born{Oppenheimer approximation [ ℄ takes advantage of the large masses of the nu
lei relative to the mass of an ele
tron. It

allows one to
ompute the low-lying vibrational states of the nu
lear motion from

knowledge of the ground state ele
tron energy level surfa
e near its minimum under the assumption that the minimum is non-degenerate. To leading order, the

vibrational energy levels are those of a harmoni
os
illator asso
iated with the

non-degenerate minimum.

1

**1991 Mathemati
s Subje
t Classi
ation. 81V55.
**

Key words and phrases. Hydrogen bonds, vibrational levels, Born-Oppenheimer approximation, semi
lassi
al normal forms.

Partially Supported by National S
ien
e Foundation Grants DMS{0303586 and DMS{

0600944.

1

2

GEORGE A. HAGEDORN AND ALAIN JOYE

**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

satises,

(1.1) E () = E + (n + 12 ) ! + (nd + 21 ) !d + O( );

where E is the minimum of the ground state ele
troni
energy level. The numbers

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

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.

In [ ℄ we propose an alternative to the Born{Oppenheimer approximation that

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 BornOppenheimer analysis. First, we s
ale the masses of the Hydrogen nu
lei as

while keeping the heavier nu
lei s
ale as . Although our analysis applies only

for small values of , the mass of a Hydrogen nu
leus is 1:015 if is dened by

taking the mass of a Carbon atom to be . This value of is roughly ' 0:082.

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( );

for some > 0, where E is an element of the spe
trum of HNF . Note that the

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 = .

Our model leads to a dierent expansion from the usual Born{Oppenheimer

approximation. For Hydrogen nu
lei

not involved in Hydrogen bonding, the vibrational energies are of order = , while the vibrational energies for the other

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

Hydrogen nu
leus involved in Hydrogen bonding at the leading order, . In the

standard Born{Oppenheimer model, all vibrational energies appear at order and

are harmoni
at that order. Anharmoni
orre
tions rst enter at order .

4

2

0

4

1

1

0

4

2

3

3

4

3

4

0

2

2

2+

2

1 2

3 2

2

2

2

4

HYDROGEN BONDS AND SEMICLASSICAL NORMAL FORMS

3

**Our analysis is motivated by an examination of symmetri
bihalide ions, su
h
**

as F HF or ClHCl , and we work under the simplifying hypothesis that bending

of the mole
ule is absent. Although symmetri
bihalide ions are quite spe
ial, our

approa
h is
exible enough to des
ribe more general phenomena. For example, the

lowest ele
tron energy surfa
e for F HF has a single minimum with the Hydrogen

nu
leus mid{way between the two Fluorines. Our general theory
an handle situations with single or
losely spa
ed double wells in the
oordinates for a Hydrogen

nu
leus that parti
ipates in Hydrogen bonding.

In this note, we further generalize our approa
h to mole
ules with nu
lei of

several dierent spe
ies, where we assume that ea
h of the masses s
ales with a

dierent inverse power of . We allow the ground state energy surfa
e to depend on

in a similar fashion as in the tri-atomi
ase, and we determine a
orresponding

normal form HNF . Then, we prove that the leading term of the vibrational levels

E () is des
ribed by HNF :

(1.3)

E () = E + O( );

for small , where

E 2 (HNF ); > 0; and > 0:

Here, the index refers to the power of in the leading term.

From a mathemati
al point view, our analysis
onsists of
onstru
ting and

studying quasimodes for the full mole
ular Hamiltonian in the singular limit ! 0.

To do this, we use a multis
ale analysis te
hnique. We identify dierent relevant

length s
ales in the system and treat them independently in the rst stage of the

analysis. This leads to a formal algorithm to
onstru
t an Ansatz for the quasimode

in more variables. We then prove that this yields a bona de quasimode for the

original problem by re-introdu
ing the
oupling between the length s
ales. This is

a traditional, su
essful route for getting information on the vibrational spe
trum

of the mole
ule. See e.g., [ ℄. In the present
ir
umstan
es, when using the same

strategy, we fa
e a new problem: The spe
trum of the normal form Hamiltonian

HNF is not known expli
itly, and we have to show that the eigenfun
tions of HNF

and their derivatives have suÆ
ent de
ay properties. For the harmoni
os
illator of

the standard Born{Oppenheimer theory, everything required is well-known.

+

4

2. The Tri{Atomi Model

**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

third nu
leus is lighter and has mass . We
onsider a simplied model in whi
h

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

has the form,

Hmol () =

2 x1 2 x2 + h(x ; x );

where x denotes the distan
e between the two identi
al nu
lei, and x is the

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

of the nu
lei. It is a self-adjoint operator on the ele
troni
Hilbert spa
e Hel . We

4

3

3

4

3

2

1

2

1

2

2

1

2

4

GEORGE A. HAGEDORN AND ALAIN JOYE

**assume h(x ; x ) has a non-degenerate ground state ele
troni
surfa
e E (x ; x )
**

with
orresponding normalized eigenve
tor (x ; x ). We further assume that the

mole
ule

a
tually binds, in the sense that that there exists a nu
lear
onguration

(xeq ; xeq ) that is an isolated minimum of E (x ; x ). We assume xeq 6= 0. (The

heavy nu
lei are not at the same point!) In the symmetri
al
ase whi
h we study

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

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

ground state ele
troni
surfa
e on . After a shift of the variable x by x , we

assume that the ground state has an expansion of the form

(2.1) E (; x ; x ) = E + a x + a x a x x + a x + O(x1 x 2 );

where ; 2 N and + 3. The Taylor series only
ontains even powers

of x , due to the symmetry of the mole
ule. The fa
tor in the harmoni
term

a x expresses the weaker binding of the Hydrogen atom. The smallness of this

oeÆ
ent makes it ne
essary to
onsider terms of order higher than quadrati
in the

expansion. We assume that a ; a and a are positive, but a
an take any eqvalue.

When a is negative, E (; x ; x ) has a
losely spa
ed double well near (x ; 0),

instead of a single lo
al minimum. Note that a = 0 leads to two de
oupled onedimensional systems, to leading order. We dene then a s
alar normal form by

keeping the leading order terms only in (2.1),

1

1

2

1

2

1

2

1

2

2

1

2

2

2

1

1

1

2

2

2

0

2

2

1

1

1

2

2

2

3

2

2

1

4

2

4

1

2

2

1

2

2

2

1

2

1

3

4

2

2

1

3

(2.2) 2 x1 2 x1 + E + a x + a x a x x + a x :

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 ) =

(x =; x = = ), we see that (2.2) minus the
onstant term E is unitarily equivalent

to times the normal form Hamiltonian HNF ,

1

1

HNF =

(2.3)

2 y1 2 y2 + ENF (y ; y )

with

ENF (y ; y ) = a y + a y

a y y +a y:

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

a ; a ; a > 0;

and either

a < 4a a ;

or

a = 4 a a and a 0:

4

1

2

2

2

3

2

0

1

2

1

2

2

2

3

1

4

4

2

1

1 2

0

2

1

Assumption

2

2

2

1

2

2

1

2

1

2

2

3

.

1

3

4

2

3

1

4

2

3

1

4

2

1

2

2

2

4

4

2

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;

(2.4)

a = 0:26; a = 1:22; a = 1:29; a = 1:62 :

The experimentally observed values [ ℄ for the symmetri
stret
h, asymmetri

stret
h, and
ombined vibrational vibrational modes are, respe
tively,

583:05
m ; 1331:15
m ; and 1849
m :

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 );

our model predi
ts the following values for these vibrational modes:

600
m ; 1399
m ; and 1942
m :

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 :

0

1

1

2

3

4

2

1

1

2

0

2

1

2

1

1

1

1

1

1

**En
ouraged by this positive numeri
al test, we turn to the mathemati
al proof
**

of assertion (1.2). It is a spe
ial
ase of the generalization (1.3), whi
h we des
ribe

in the next se
tion.

3. More mass s
ales

The tri{atomi
model presented in [ ℄ and its mathemati
al analysis generalize naturally. Roughly speaking, we
an
onsider mole
ules with nu
lei of several

dierent spe
ies, where we assume that ea
h of the masses s
ales with a distin
t

inverse power of . The
orresponding ground state energy surfa
e depends on in

a similar way to the tri-atomi
ase.

We adopt this more general point of view here and prove the leading order

result (1.3) whi
h generalizes (1.2). More pre
isely, we work under the following

general assumption.

3.1 Let Hmol() be a self-adjoint mole
ular Hamiltonian dened

on a domain of L (Rn ; Hel ) by

3

Assumption

.

2

(3.1)

Hmol ()

=

n

X

j =1

j

2

x2j

+ h(; x);

1 2 n > 0:

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 eigenvalue 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 ;

v () 2 R;

1

6 2Nn

where the
oeÆ
ients v () are regular as ! 0.

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) =

(x =1 ; ; xn=n ), whi
h we denote by y = x=.

+

1

1

n

X

j

=

2

2 y ; for some > 0:

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

V (; y)

(3.4)

v () ( = ) jj y ;

j =1

x2j

1 2

(

+2)

6 2Nn

0=

**where we use the notation = Pnj j j and jj = Pnj j . As in the
**

tri-atomi
ase, we want VNF to
onsist of the terms on the right hand side

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:

3.2 There exist > 0 and two non-empty nite sets of multiindi
es, Nn n f0g and F Nn n , su
h that for small jxj and ,

=1

Assumption

0

.

V

(3.5)

=1

0

0

(; x)

X

2 0

v ()

**for some
> 0. Furthermore,
**

8

< v () ( = ) j j

(3.6)

:

(j j + 2)

1 2

(

+2)

x

=

;

>

0;

X

x

2 F

8 2

8 2 F :

0

**3.3 We address the question of existen
e of a suitable and the
**

orresponding sets and F for a given general potential at the end of this se
tion.

Remark

.

0

HYDROGEN BONDS AND SEMICLASSICAL NORMAL FORMS

7

**3.4 The
ase of the tri-atomi
mole
ule in R is
hara
terized by the
**

parameters = 4; = 3; = 1; = 1=2; = 2; and the sets

= f(2; 0); (0; 2); (1; 2); (0; 4)g;

F = f(3; 0); (2; 2); (1; 4); (0; 6)g;

for whi
h (jj + 2) = 2 for all 2 F .

Remark

2

.

1

2

1

2

0

**3.5 For any 0 < < n, the last
ondition in (3.6) is always satised
**

for large enough jj, sin
e by (3.1) and (3.3),

(j j + 2) (n )) j j 2 = 2 (nj j ):

The normal form potential is then dened as

X

(3.7)

y ;

VNF (y) =

Remark

.

2 0

**so that the s
alar normal form Hamiltonian be
omes
**

1 + VNF :

HNF =

2

Taking into a
ount our normalization (3.2), we expe
t the spe
trum of Hmol() to

ontain elements of the form

(3.8)

E () = E + O( );

for small , where

(3.9)

E 2 (HNF ) and > 0:

The index refers to the power of in the leading term.

Let us brie
y
onsider the existen
e of a suitable normal form for a given smooth

potential of the form (3.4) and, in parti
ular, the denition of the exponent > 0.

Consider the usual situation in whi
h at least one monomial in the Taylor expansion

(3.4) whose
oeÆ
ient is independent of appears in the normal form. Su
h terms

must dene the exponent , be
ause they
ontain no extra dependen
e, and after

res
aling, their
ontribution to the normal form
annot diverge. Thus, we introdu
e

the set

N = f 2 N n : v () =
6= 0g:

The dimensions
orresponding to the minimal value n of the exponents j play

a spe
ial r^ole. Let 0 k n be the integer su
h that n = n = n k <

n k . We dene

k = f 2 N n : = (0; ; 0; n k ; n k ; ; n ) (0; ; 0; 00 )g:

Similarly, we write x00 = (0; ; 0; xn k ; xn k ; ; xn ). 00For simpli
ity, we assume 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).

+

1

1

+1

+1

8

GEORGE A. HAGEDORN AND ALAIN JOYE

3.6 Assume N \ k 6= ;. Then Assumption 3.2 holds with

< n ;

= min

2N 2 + j j

Proposition

.

= f 2 Nn : (2 + jj) 0 g;

and

F = f 2 N n n : j j < F g

for some suÆ
iently large F > 0, provided

v () ( = ) jj

=
; 8 2 n N :

0

0

1 2

Remark

Proof.

(

+2)

0

**3.7 A
tually, F = max 20 jj + 1 will do.
**

.

Observe that for jj xed,

2 + j j

2j+j jnj

with equality if and only if 2 k. Sin
e x 7! 2x+nx is stri
tly in
reasing, we have

j 00 j n :

j n > 00 min

2N \k 2 + j 00 j

Moreover, this shows that the minimum over N is rea
hed on the nite set f 2

N n : j j min00 2k j 00 j g. Then, Remark 3.5 implies that is nite. Moreover,

for any 2 N ; (2 + jj) 0. Hen
e, the
orresponding terms in the

0

**Taylor series either
ontribute to the normal form, or they are of higher order and
**

an be negle
ted. The last
ondition ensures that the dependen
e of the
oeÆ
ents

is strong enough to
ompensate for the negative exponents (jj + 2).

4. Mathemati
al properties of

HNF

**The normal form Hamiltonian HNF plays the same r^ole that the harmoni
**

os
illator plays in the standard Born{Oppenheimer approximation. However, in

ontrast with the harmoni
os
illator, we do not know the spe
tral properties of

HNF expli
itly. In [ ℄ we prove
ertain properties that we require for our analysis.

We now des
ribe them.

We
onsider S
hrodinger operators with potentials that satisfy the following

hypothesis.

4.1 Let H = + V be self-adjoint on a suitable domain

n

in L (R ), where x 7! V (x) is a polynomial and V 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)

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

absen
e of essential spe
trum for S
hrodinger operators with polynomial potentials

an be found in [ ℄ . Within our framework, it states the following:

3

Assumption

2

1

2

.

1

3

7

1 We

1

thank B. Heler for pointing this riterion out to us.

HYDROGEN BONDS AND SEMICLASSICAL NORMAL FORMS

**For a polynomial V 0, dene
**

mV (x) = 1 +

(4.1)

where

D

=

2Nn

jD V (x)j;

**. Note that the sum is nite.
**

4.2 ([ ℄, Thm (1.3)) Let H satisfy Assumption 4.1 and let mV

x11 x22

Proposition

X

9

xnn

7

.

be dened by (4.1). Then, the resolvent of H is ompa t if and only if

lim mV (x) = 1:

4.3 The proof of this result in [ ℄ nds its roots in earlier work on

hypoellipti
operators. See e.g. [ ℄.

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

(4.2)

E (x ; x ) = a x + a

a x x + a x;

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
orresponding fun
tion mNF diverges at innity.

We also need to know that the eigenfun
tions de
ay exponentially, in a L

sense, together with their derivatives. This is the
ontent of the next result whi
h

is proven in [ ℄.

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,

for any a > 0,

' 2 D(eahxi); r' 2 D(eahxi ); and ' 2 D(eahxi );

P

where hxi = (1 + nj xj ) = , and D(eahxi ) denotes the domain of the operator

jxj!1

Remark

.

7

5

NF

NF

1

2

1

1

2

2

1

2

3

1

2

2

4

2

4

2

3

Proposition

.

2

=1

2 1 2

multipli ation by eahxi .

The smoothness of the eigenfun
tions follows from ellipti
regularity arguments. Their exponential de
ay properties are
onsequen
es of
lassi
al

Combes{Thomas arguments. Sin
e the potential is a polynomial, we immediately dedu
e the exponential de
ay of ' by using the eigenvalue equation. That

r' 2 D(eahxi) is a
onsequen
e of the following lemma, with p(x) = eahxi:

4.5 Let x 7! p(x) 2 C (Rn ) be positive, and assume that there exists

n

a
onstant C < 1, su
h that Rj(rp(x))=p(x)j 2 C for

all x 2 R .

Then, for any f 2 g : Rn jg (x)j + jg (x)j p(x) dx < 1

q

(4.3) kp = rf k C kp = f k + kp = f k kp = f k + C kp = f k :

The rather te
hni
al proof of this lemma
an be found in [ ℄.

4.6 While Proposition 4.4 is suÆ
ient to derive the leading
ontribution (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

eigenfun
tion:

Proof.

Lemma

1

.

2

1 2

1 2

2

1 2

1 2

2

3

Remark

.

1 2

1 2

2

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 [ ℄.

4.8 We also note that while the exponential de
ay properties of

eigenfun
tions of S
hrodinger operators have been the obje
t of many detailed and

rened investigations (See e.g., [ ℄), we
ould not nd any published results that

dealt with the de
ay properties of their su
essive derivatives.

3

Remark

.

6

5. Leading order results

**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.

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

+ VNF , with VNF dened by

normal form S
hrodinger operator HNF =

3

Theorem

.

mol

1

2

**(3.7). Further assume that the polynomial VNF is bounded below, and that HNF
**

has
ompa
t resolvent.

Let f 2 L2 (Rn ) be a normalized eigenve
tor
orresponding to an eigenvalue E

of HNF

(5.1)

Then, for small ,

satises

for some > 0.

1 + V (y) f (y) = E f (y):

2 y NF

there exists an element E () of the spe
trum of H () that

E () = E + O( ):

mol

+

**5.2 The tri-atomi
results are dire
t
onsequen
es of this result, up
**

to a res
aling of the energy.

5.3 Theorem 5.1 applies in parti
ular to s
alar S
hrodinger operators

with potential V () satisfying Assumption 3.2.

5.4 In the
ase of the tri-atomi
mole
ule, it is possible to go beyond

leading order results. Theorem 3.7 in [ ℄ states the existen
e a
omplete asymptoti

expansion in powers of = for E ().

We
onstru
t a quasimode based on the elements above. This quasimode is supported
lose to the origin of the
oordinates, and we introdu
e a
uto

fun
tion F on Rn , dened as follows:

(5.2)

F (z ; ; zn ) = F (z ) F (z ) F (zn )

1

where F () 2 C (R; [0; 1℄) is even, supported on [ 2; 2℄, and equal to 1 on [ 1; 1℄.

We introdu
e a set of exponents (Æ ; ; Æn) with

(5.3)

0 < Æj < j ; 8 j = 1; 2; ; n;

Remark

.

Remark

.

Remark

.

3

1 2

Proof.

1

1

1

2

HYDROGEN BONDS AND SEMICLASSICAL NORMAL FORMS

11

**whose values will be determined in the
ourse of the proof. We also use the shorthand notation x=Æ = (x =Æ1 ; ; xn =Æn ).
**

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

(1 F (x=Æ )) jf (x= )j dx:

n

1

2

2

2

2

R

R

The rst term is equal to jj by s
aling. Using the exponential de
ay of f , Proposition 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

Z

P

P

a nj=1 jyj j e a nj=1 jyj j jf (y )j dy

j

j

j

f

(

x=

)

j

dx

e

Æj

Æj j

2

jxj j

2

jyj j

jj e

2

P

a nj=1 1=j Æj

2

kea

Pnj

=1

2

jyj j f k2

(5.6)

= O(1 ):

Altogether, this shows that k Q(; x)k = jj= (1 + O(1 )). Thus, to prove the

result, we need only show that

(5.7)

kHmol () Q () E Q ()k = O(jj= );

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

2

2+ +

R(; x) =

+

(5.9)

+

n

X

j =1

n

X

j =1

n

X

j =1

j (x) f (x= ) x2j F (x=Æ )=2

j xj ((x) f (x= )) xj F (x=Æ )

j f (x= ) x2j (x)=2

+ xj f (x=) xj (x) F (x=Æ ):

**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

are O(1). The last
ontribution to R() is simply estimated

Pn

j

j

=

**by O( j j j ), where jj=
omes from s
aling. By (3.3), j j =
**

+ j > , so that R() satises the bound (5.7). To bound the norm of the rst

=1

2

2

12

GEORGE A. HAGEDORN AND ALAIN JOYE

**term in (5.8), we use (3.5) and (3.7) to see that
**

k(V () VNF (= )) Q ()k

X

Z

jxj j2Æj

2F

jx j jf (x= )j dx

2

! 1 =2

2

(5.10)

~ jj= Æ ;

for some
onstant
~. By assumption, for all 2 F , we have

= ( (j j + 2)) > 0. Hen
e, by
ontinuity,
hoosing Æj < j
lose

to j , we get

jj= Æ = jj= Æ jj= ;

with > 0;

whi
h ends the proof.

5.5 From the proof, we get that the quasimode for the tri-atomi

mole
ule is of the form

(5.11)

Q(; x ; x ) = (x ; x ) f (x =; x = = ) F (x =Æ1 ; x =Æ2 );

for suitable values of Æ and Æ , and where f is an eigenfun
tion of the normal form

(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.

2

1

2

2

Remark

2+

2+

.

1

2

1

1

2

1

2

1 2

1

2

2

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 Hydrogen 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

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