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**Asso
iated with Hydrogen Bonds
**

I:

The Symmetri Case

George A. Hagedorn

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.

Alain Joye

Institut Fourier

Unite Mixte de Re
her
he CNRS-UJF 5582

Universite de Grenoble I, BP 74

F{38402 Saint Martin d'Heres Cedex, Fran
e

and

Laboratoire de Physique et Modelisation des Milieux Condenses

UMR CNRS-UJF 5493, Universite de Grenoble I, BP 166

38042 Grenoble, Fran
e

February 22, 2007

Abstra
t

We propose an alternative to the usual time{independent Born{Oppenheimer approximation that is spe
i
ally designed to des
ribe mole
ules with symmetri
al Hydrogen bonds. In our approa
h, the masses of the Hydrogen nu
lei are s
aled dierently

from those of the heavier nu
lei, and we employ a spe
ialized form for the ele
tron energy level surfa
e. Consequently, anharmoni
ee
ts play a role in the leading order

al
ulations of vibrational levels.

Although we develop a general theory, our analysis is motivated by an examination

of symmetri
bihalide ions, su
h as FHF or ClHCl . We des
ribe our approa
h for

the FHF ion in detail.

Partially

Supported by National S ien e Foundation Grants DMS{0303586 and DMS{0600944.

1

1 Introdu
tion

In standard Born{Oppenheimer approximations, the masses of the ele
trons are held xed,

and the masses of the nu
lei are all assumed to be proportional to 4. Approximate solutions

to the mole
ular S
hrodinger equation are then sought as expansions in powers of . For

the time{independent problem, the ele
tron energy level surfa
e is also assumed to behave

asymptoti
ally like a quadrati
fun
tion of the nu
lear variables near a lo
al minimum.

In this paper and in a future one [4℄, we propose an alternative approximation for

mole
ules that
ontain Hydrogen atoms as well as some heavier atoms, su
h as Carbon,

Nitrogen, or Oxygen. Our motivation is to develop an approa
h that is spe
i
ally tailored

to des
ribe the phenomenon of Hydrogen bonding.

In this paper, we examine the spe
i
ase of systems with symmetri
Hydrogen bonds,

su
h as F HF . In [4℄, we plan to study non{symmetri
ases, where the stru
ture of the

typi
al ele
tron energy surfa
e is very dierent. The mathemati
al analysis of that situation

is
onsequently
ompletely dierent.

The model we present here diers from the usual Born{Oppenhimer model in two ways:

1. We s
ale the masses of the Hydrogen nu
lei as 3 instead of 4 . This is physi
ally

appropriate. If the mass of an ele
tron is 1, and we dene 4 to be the mass of a C 12

nu
leus, then = 0:0821, and the mass of a H 1 nu
leus is 1:015 3.

2. We do not assume that the ele
tron energy level is well approximated by an {independent

quadrati
fun
tion near a lo
al minimum. Instead, we allow it to depend on and to

take a parti
ular form that we spe
ify below. The parti
ular form we have
hosen is

motivated by a detailed examination of the lowest ele
troni
potential energy surfa
es

for F HF and ClHCl .

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

model
an handle situations with single or double wells in the
oordinates for a Hydrogen

nu
leus that pati
ipates in Hydrogen bonding. We hope that the ideas in this paper and [4℄

might provide some insight into some properties of Hydrogen bonded systems.

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

2

of order 3=2 , while the vibrational energies for the other nu
lei and the Hydrogen nu
lei involved in the symmetri
Hydrogen bonding are of order 2 . Furthermore, anharmoni
ee
ts

must be taken into a
ount for a Hydrogen nu
leus involved in Hydrogen bonding at their

leading order, 2. In the standard Born{Oppenheimer model, all vibrational energies appear

in a harmoni
approximation at order 2. Anharmoni
orre
tions enter at order 4 .

We present our ideas only in the simplest possible situation. In that situation, there are

only 3 nu
lei, and they are
onstrained to move along a xed line. We plan to study more

general possibilities, su
h as bending of the mole
ule, in the future.

The paper is organized as follows: In Se
tion 2, we present the formal expansion. In

Se
tion 3 we state our rigorous results as Theorems 3.7 and 3.8. The proofs of some te
hni
al

results are presented in Se
tion 4.

The authors would like to thank Thierry Gallay for several helpful
onversations, and Bernard Heler and the referees for pointing out Proposition 3.2 to

them. George Hagedorn would like to thank T. Daniel Crawford for tea
hing him to use the

Gaussian software of
omputational
hemistry.

A
knowledgements

**2 Des
ription of the Model
**

We study a triatomi
system with two identi
al heavy nu
lei A and B , and one light

(Hydrogen) nu
leus C . We begin by des
ribing the Hamiltonian for this system in Ja
obi
oordinates. We let xA and xB be the positions of the heavy nu
lei, and let xC be

the position of the light nu
leus C . We let their masses be mA = mB and mC . We

let R = mAxmA ++mmB xB++mmC xC denote the
enter of mass of all three nu
lei, and let

A

B

C

xA + xB

xAB =

2 denote the
enter of mass of the heavy nu
lei. We let W = xB xA

be the ve
tor from nu
leus A to nu
leus B and let Z = xC xAB be the ve
tor from the

enter of mass of A and B to C . We assume the ele
troni
Hamiltonian he only depends on

the ve
tors between the nu
lei, and we set mAB = mA + mB and M = mA + mB + mC . In

the original variables, the Hamiltonian has the form

1

1 + h (x x ; x x ; x x ):

1

x

x

e B

A C

A C

B

2 mA

2 mB

2 mC x

A

B

C

3

**In these Ja
obi
oordinates, it has the form
**

1

mAB

M

R

W

2M

2 mA mB

2 mAB mC Z + he(W; Z + W=2; Z W=2):

Sin
e we are interested in bound states, we dis
ard the kineti
energy of the
enter of mass.

We take the ele
tron mass to be 1, and the masses of the heavy nu
lei to be mA = mB = 4 ,

for some xed . The mass of the light nu
leus is mC = 3 , for some xed . The ele
troni

Hamiltonian he then be
omes he(W; Z + W=2; Z W=2) h(W; Z ), so that the Hamiltonian

of interest is

4

W

3

2

1 + 2

Z + h(W; Z ):

**This
omputation is exa
t and valid in any dimension.
**

To simplify the exposition, we drop the term 2 in the fa
tor that multiplies Z . It

gives rise to uninteresting, regular perturbation
orre
tions. Also, for simpli
ity, we assume

= 2 and = 1. This
an always be a
omplished by trivial res
alings of W and Z .

To des
ribe our ideas in the simplest situation, we restri
t W and Z to one dimension.

Thus, we are not allowing rotations or bending of the mole
ule. Furthermore, we introdu
e

dependen
e of the ele
troni
Hamiltonian to model the pe
ularities of symmetri
Hydrogen

bonds that we des
ribe below.

These
onsiderations lead us to study the Hamiltonian

4 2

2 W 2

3 2

H1 () =

(2.1)

2 Z 2 + h(; W; Z ):

The ele
tron Hamiltonian h(; W; Z ) is an operator in the ele
troni
Hilbert spa
e that depends parametri
ally on (; W; Z ) and in
ludes the nu
lear repulsion terms. For
onvenien
e,

we assume that h(; W; Z ) is a real symmetri
operator.

We now des
ribe the spe
i
dependen
e of h(; W; Z ) that we assume. Although the

ele
tron Hamiltonian does not depend on nu
lear masses, the parameter is dimensionless,

and thus may play more than one role. The dependen
e of h on we allow is motivated by the

**smallness of a parti
ular Taylor series
oeÆ
ient we observed in numeri
al
omputations for
**

the ground state ele
tron energy level for the real system F HF . We allow only the ground

state eigenvalue to depend on . Otherwise, our ele
tron Hamiltonian is {independent. With

the physi
al value of inserted in our Hamiltonian, we obtain the true physi
al Hamiltonian.

From numeri
al
omputations of E (W; Z ) for F HF , we observed that the Z 2
oeÆ
ient

in the Taylor expansion about the minimum (W0 ; 0) of the ground state potential energy

4

**surfa
e had a small numerial value, on the order of the value of = 0, where 0 was dened
**

by setting 0 4 equal to the nu
lear mass of the C 12 isotope of Carbon.

The value of 0 is roughly 0.0821. We dene a2 so that the true Z 2 Taylor series term is

a2 0 Z 2 . We then obtain h(; W; Z ) by adding ( 0 ) a2 Z 2 to the ground state eigenvalue

E (W; Z ). We make no other alterations to the ele
tron Hamiltonian. When = 0 , our

h(; W; Z ) equals the true physi
al ele
tron Hamiltonian h(0 ; W; Z ).

Thus, we assume the ground state ele
tron level has the spe
i
form

E1 (; W; Z )

=

E0

+ a1 (W

W0 )2

+

a3 (W

a2

W0 ) Z 2

+ a4 Z 4 + ; (2.2)

**with aj = O(1). As we shall see, the leading order behavior of the energy and the wave
**

fun
tions for the mole
ule are determined from the terms written expli
itly in (2.2). The

terms not expli
itly displayed are of orders (W W0 ) Z 2 , where and are non-negative

integers that satisfy + 3. They play no role to leading order, but
ontribute to higher

order
orre
tions.

We assume a1, a3 , and a4 are positive, but that a2
an be positive, zero, or negative.

When a2 is negative, E1 (; W; Z ) has a
losely spa
ed double well near (W0 ; 0) instead of a

single lo
al minimum.

To ensure that the leading part of E1(; W; Z ),

Ee1 (; W; Z )

=

E0

+ a1 (W

W0 )2

+

a3 (W

a2

W0 ) Z 2

+ a4 Z 4 ;

**is bounded below, we assume that either
**

a23 <

or

a23

4 a1 a4 ;

(2.3)

= 4 a1 a4

and

a2

0:

(2.4)

**These
onditions are equivalent to the property Ee1(; W; Z )
**

an write

Ee1

(; W; Z ) =

a1

By res aling with w = (W

(W

W0 )

a3 2 2

2a1 Z

+

a4

a23

4a1

C

**for some C , sin
e we
**

Z4

+

a2 Z 2 :

**W0 )= and z = Z=1=2 , we see that the Hamiltonian
**

4 2

2 W 2

3 2

2 Z 2

5

+

Ee1 (; W; Z )

**is unitarily equivalent to 2 times the {independent Normal Form Hamiltonian
**

1

2

2

1

HNF =

2 w2 2 z2 + ENF(w; z);

where

ENF (w; z ) = a1 w2 + a2

a3 w z 2 + a4 z 4 :

(2.5)

(2.6)

**Although we do not use it, further s
aling shows that HNF is essentially a three{
**

parameter model, sin
e the
hange of variables w = s, z = t, yields

1

1

2

2

2

2

2

2

4

HNF '

2 s2 2 t2 + 1 s + 2 t 3 s t + t ;

with

a

a

a

= a4 1=6 ; 1 = 2=13 ; 2 = 22=3 ; and 3 = 53=6 :

Remark

a4

a4

a4

**Under
onditions (2.3) or (2.4), HNF is essentially self-adjoint on C01(IR2 ) and has purely
**

dis
rete spe
trum. This last property is easy to verify under
ondition (2.3), or
ondition

(2.4) with a2 > 0, be
ause ENF(w; z) tends to innity as k (w; z) k ! 1. When (2.4) is

satised with a2 = 0, the result is more subtle be
ause ENF (w; z) attains its minimum value

of zero along a parabola in (w; z). In that
ase we prove that the spe
trum is dis
rete in

Proposition 3.1.

The expression (2.2) is
learly spe
ial. Our
omputations for F HF that motivate this expression have roughly the following values, where

distan
es are measured in Angstroms and energies are measured in Hartrees:

W0 = 2:287;

E0 = 200:215;

a1 = 0:26;

a2 = 1:22

( if = 0:0821 );

a3 = 1:29;

a4 = 1:62:

These results
ame from tting the output from Gaussian 2003 using se
ond order Moller{

Plesset theory with the aug{
{pvtz basis set. We observed that the pro
ess of tting the

Expli
it Computations for FHF

6

**data was numeri
ally quite unstable, and that
ondition (2.3) was barely satised by these
**

aj .

0.4

Displacement of H from F − F Center of Mass

0.3

0.2

0.1

0

−0.1

−0.2

−0.3

−0.4

2.1

2.2

2.3

2.4

F − F Distance

2.5

**Contour plot of the ground state ele
troni
potential energy surfa
e in the Ja
obi
**

oordinates (W,Z). It is obviously not well approximated by a quadrati
. Our te
hnique

exploits the
atness of the surfa
e in the Z dire
tion near the minimum.

Figure 1.

The experimentally observed values [11℄ for the ex
itation energies to the rst symmetri
stret
hing vibrational mode and the rst asymmetri
vibrational mode of F HF are

583:05
m 1 and 1331:15
m 1, respe
tively. With the values of aj above, the leading order

7

**al
ulation from our model predi
ts 600
m 1 and 1399
m 1. By leading order, we mean
**

E0 + 2 E2 in the expansion we present below. These values depend sensitively on pre
isely

how we t the potential energy surfa
e, whi
h itself depends sensitively on the ele
tron

stru
ture
al
ulations. By
omparison, Gaussian 2003 with the aug-
-pvdz basis set predi
ts harmoni
frequen
ies of 608
m 1 and 1117
m 1 . We
ould not obtain frequen
ies for

the aug-
-pvtz basis set from Gaussian be
ause of our
omputer limitations.

For some very re
ent numeri
al results for vibrational frequen
ies of F HF that appeared

as we were nishing this paper, see [2℄.

We now mimi
the te
hnique of [3℄ to obtain an expansion for the solution to the eigenvalue problem for (2.1). We
ould have used the te
hnique of [5℄, but that would have led

to more
ompli
ated formulas.

For
onvenien
e, we repla
e the variable W by W W0 , so that hen
eforth, W0 = 0.

The te
hnique of [3℄ uses the method of multiple s
ales. Instead of sear
hing dire
tly for

an eigenve
tor (; W; Z ) for (2.1), we rst sear
h for an eigenve
tor (; W; Z; w; z) for an

operator that a
ts in more variables. When we have determined , we obtain by setting

(; W; Z ) = (; W; Z; W=; Z=1=2 ):

This is motivated physi
ally by the following observation: The dependen
e of the ele
trons

on the nu
lear
oordinates o
urs on the length s
ale of (W; Z ), while the semi
lassi
al

quantum
u
tuations of the nu
lei o
ur on the length s
ale of (w; z). To leading order in

, these ee
ts behave independently.

The equation for is formally

H2 ()

(; W; Z; w; z) = E () (; W; Z; w; z);

where

H2 ()

4 2

2 W 2

=

3

+ [ h(; W; Z )

+

1

X

m=6

m=2

2

W w

2 2

2 w2

E (; W; Z ) ℄

Tm=2 (W; Z )

3 2

2 Z 2

(2.7)

5=2

2

Z z

2 2

2 z2

+ E (; w; 1=2 z)

Tm=2 ( w; 1=2 z ) :

8

(2.8)

**The fun
tions Tm=2 in this expression will be
hosen later. Dierent
hoi
es yield equally
**

valid expansions for (; W; Z ), although they alter the expressions for (; W; Z; w; z) by

onverting (W; Z ) dependen
e into (w; z) dependen
e.

In (2.8), we expand both E (; w; 1=2 z) and Tm=2 (w; 1=2 z) in Taylor series in powers

of 1=2 . We then make the Ansatz that (2.7) has formal solutions of the form

(; W; Z; w; z) = 0 (W; Z; w; z) + 1=2 1=2 (W; Z; w; z) + 1 1(W; Z; w; z) + ; (2.9)

with

E () = E0 + 1=2 E1=2 + 1 E1 + :

(2.10)

We substitute these expressions into (2.7) and solve the resulting equation order by order in

powers of 1=2 .

The des
ription in this se
tion is purely formal. In parti
ular, it does not take into

a
ount the
utos that are ne
essary for rigorous results. The mathemati
al details are

dealt with in the next se
tion.

Note:

**The order 0 terms require
**

[ h(; W; Z ) E (; W; Z ) ℄ 0 + E0 0 = E0 0 :

We solve this by
hoosing

E0 = E0;

and

0 (W; Z; w; z ) = f0 (W; Z; w; z ) (W; Z );

where (W; Z; ) is a normalized ground state eigenve
tor of h(; W; Z ). Under our assumptions, we
an
hoose (W; Z; ) to be real, smooth in (W; Z ), and independent of .

This
hoi
e satises

h (W; Z; ); rW;Z (W; Z; ) iH = 0;

(2.11)

where the inner produ
t is in the ele
troni
Hilbert spa
e. We assume that f0(W; Z; w; z)

is not identi
ally zero.

Order 0

el

=

Order 1 2

**The order 1=2 terms require
**

[ h(; W; Z ) E (; W; Z ) ℄ 1=2 +

9

E0 1=2

= E0

1=2

+ E1=2

0:

**The
omponents of this equation in the (W; Z ) dire
tion in the ele
troni
Hilbert spa
e
**

require

E1=2 = 0:

The
omponents of the equation orthogonal to (W; Z ) in the ele
troni
Hilbert spa
e require

[ h(; W; Z )

so

1=2 (W;

=

Orders 1 and 3 2

Z; w; z )

E (; W; Z ) ℄ 1=2

=

= 0;

f1=2 (W; Z; w; z ) (W; Z ):

**By similar
al
ulations, the order 1 and 3=2 terms yield
**

E1 = E3=2 = 0;

1 (W;

Z; w; z )

=

f1 (W; Z; w; z ) (W; Z );

3=2 (W;

Z; w; z )

=

f3=2 (W; Z; w; z ) (W; Z ):

Order 2

require

and

The order 2 terms that are multiples of (W; Z ) in the ele troni Hilbert spa e

1 2 f0 (W; Z; w; z)

2 w2

= E2 f0 (W; Z; w; z);

1

2

2 f0

(W; Z; w; z)

z 2

+

ENF (w; z ) f0 (W; Z; w; z )

(2.12)

**where ENF(w; z) is given by (2.6).
**

Be
ause of the form of ENF(w; z), (2.12) does not separate into two ODE's. We do

not know E2 or f0 exa
tly, although a
urate numeri
al approximations
an be found easily.

These eigenvalues and eigenfun
tions des
ribe the
oupled anharmoni
vibrational motion

of all three nu
lei in the mole
ule. As we
ommented earlier, hypotheses (2.3) or (2.4)

guarantee that the eigenvalues E2 are dis
rete and bounded below, with normalized bound

states f0 (W; Z; w; z) in (w; z) for any (W; Z ).

Later in the expansion, we
hoose the operator T3 so that f0 has no (W; Z ) dependen
e.

With this in mind, equation (2.12) determines E2 and a normalized fun
tion f0(w; z) (up to

a phase) for any given vibrational level.

10

**The terms of order 2 that are orthogonal to (W; Z ) require
**

[ h(; W; Z )

E (; W; Z ) ℄ 2

= 0;

Thus,

= f2(W; Z; w; z) (W; Z ):

We split the s
alar fun
tions f (W; Z; w; z) with > 0 into two
ontributions

2

f (W; Z; w; z )

= fk(W; Z; w; z) +

f?(W; Z; w; z )

**where for ea
h xed W and Z , fk(W; Z; ; ) is a multiple of f0 (; ), and f?(W; Z; ; )
**

perpendi
ular to f0(; ) in L2(R 2 ; dw dz). Furthermore, we
hoose the operators T3+m=2

later in the expansion so that fk(W; Z; ; ) has no (W; Z ) dependen
e. We will not pre
isely

normalize our approximate eigenfun
tions, so we hen
eforth assume fk (W; Z; w; z) = 0 for

all > 0.

We equate the terms of order m=2 and then separately examine

the proje
tions of the resulting equation into the (W; Z ) dire
tion in the ele
tron Hilbert

spa
e and into the dire
tion perpendi
ular to (W; Z ).

From the terms in the (W; Z ) dire
tion, we obtain the value of Em=2 and an expression

for f(m 4)=2 (W; Z; w; z) = f(?m 4)=2 (W; Z; w; z). When m = 6 we
hoose T3 so that f0
an

be
hosen independent of (W; Z ). When m > 6, we
hoose Tm=2 , so that f(km 6)=2
an be

taken to be zero.

The terms orthogonal to (W; Z ) in the ele
troni
Hilbert spa
e give rise to an equation

for [ h(; W; Z ) E (; W; Z ) ℄ m=2 . This equation has a solution of the form

=

Order m 2 with m

>4

m=2 (W; Z; w; z ) =

k (W; Z; w; z )

fm=

2

+

?

m=2

+

? (W; Z; w; z )

fm=

2

(W; Z )

(W; Z; w; z);

**? is obtained by applying the redu
ed resolvent operator [ h(; W; Z )
**

where m=

2

to the right hand side of the equation.

E (; W; Z ) ℄r 1

**In the next se
tion, we prove that this pro
edure yields a quasimode whose approximate
**

eigenvalue and eigenve
tor ea
h have asymptoti
expansions to all orders in 1=2 .

11

3 Mathemati
al Considerations

In this se
tion we present a mathemati
ally rigorous version of the expansion of Se
tion 2.

This involves inserting
utos and proving that many te
hni
al
onditions are satised at

ea
h order of the expansion.

Assume (2.3) or (2.4).

1 2

Then, the spe
trum of HNF =

2 w2

Proposition 3.1

1 2 +

2 z2

ENF (w; z ) is purely dis rete.

This proposition is an easy
onsequen
e of the following general
riterion [12℄ that guarantees that the spe
trum of + V is dis
rete for
ertain polynomials V . This
riterion

nds its roots in earlier work on hypoellipti
operators. (See e.g., [9℄.)

([12℄, Thm 1.3) Let V (x) 0 be a non-negative polynomial in x 2 IRn .

Proposition 3.2

Dene

mV (x)

X

jDV (x)j;

2Nn

n

1

2

x1 x2

xn , and the sum is nite. Let H

L2 R n . Then the resolvent of H is
ompa
t if and

where

=

domain in (

D

=1+

= + V be self-adjoint on a

only if limjxj!1 mV (x) = 1.

)

**One easily
he
ks that limjxj!1
**

immediate
onsequen
e of Prop. 3.2.

Proof of Prop. 3.1

mENF (x)

= 1, so Prop. 3.1 is an

**In the usual Born{Oppenheimer approximation, the semi
lassi
al expansion for the nu
lei
**

is based on Harmoni
os
illator eigenfun
tions. They have many well-known properties.

Our expansion relies on the analogous properties for eigenfun
tions of HNF . The following

proposition establishes some of the properties we need in an even more general setting.

Let V be a non-negative polynomial, su
h that H = + V has purely

dis
rete spe
trum. Let '(x) be an eigenve
tor of H , i.e., an L2 (R n ) solution of H' = E ',

where E > 0. Then, ' 2 C 1 (IRn ) and r' 2 L2 (IRn ). Moreover, for any a > 0,

Proposition 3.3

where hxi =

v

u

u

t

' 2 D(eahxi );

1+

n

X

j =1

r' 2 D(eahxi );

and

' 2 D(eahxi );

x2j , and D(eahxi ) denotes the domain of multipli ation by eahxi .

12

**Sin
e V 2 C 1, ellipti
regularity arguments (see e.g., [8℄, Thm 7.4.1) show that all
**

eigenfun
tions are C 1.

We rst show that the r' is L2 . Sin
e V 0, the quadrati
form dened by

p

p

h('; ) = h r'; r i + h V '; V i

Proof

**on Q(h) = Q( ) \ Q(V ), is
losed and positive. Here Q(A) means the quadrati
form
**

domain of the operator A. Sin
e D(H ) Q(h), any eigenve
tor of H belongs to

Q(

) = f ' 2 L2(IRn) : k r' k < 1 g:

Thus, r' 2 L2 .

Next, we prove ' 2 D(eahxi ), for any a > 0 by a Combes{Thomas argument, as presented

in Theorem XII.39 of [15℄. We des
ribe the details for
ompleteness. Let 2 IR, and let v

denote xj for any j 2 f1; ; ng. We
onsider the unitary group W () = eiv for 2 IR,

and
ompute

H ( )

=

W ( ) (

+ V ) W ( ) 1 =

H

+

i v

+

2 :

**The operator iv is H -bounded, with arbitrary small relative bound, sin
e V 0. Thus
**

fH ()g extends a self-adjoint, entire analyti
family of type A, dened on D(H ). We note

that sin
e H (0) = H has purely dis
rete spe
trum, its resolvent, R0 () is
ompa
t, for any

2 (H ) CI n (H ). Hen
e, R () = (H () ) 1 is
ompa
t for any 2 IR, and

hen
e, for all 2 CI , if 2 (H ()). It is jointly analyti
in and . The eigenvalues

of H () are thus analyti
in , ex
ept at
rossing points, where they may have algebrai

singularities. Sin
e for real, W () is unitary, the eigenvalues are a
tually independent of

, and (H ()) = (H ), for any .

Let P be the nite rank spe
tral proje
tor
orresponding to an eigenvalue E of HNF .

Then, for 2 IR, P () = W ()P W () 1 is the spe
tral proje
tor
orresponding to the

eigenvalue E of H (). By Riesz's formula and the properties of the resolvent, P () extends

to an entire analyti
fun
tion that satises

W (0 )P ()W (0) 1 = P (0 + ):

for any 0 2 IR.

By O'Connor's Lemma (Se
t. XIII.11 of [15℄), this yields information about the eigenve
tors. If ' = P ', the ve
tor ' = W ()', dened for 2 IR has an analyti
extension to the

13

**whole
omplex plane, and is an analyti
ve
tor for the operator v. Therefore, ' P2 D(eajvj),
**

for any a > 0. By taking all possible xj 's for v, and noting that D(eahxi ) = D(ea( jx j) ), we

see that ' 2 D(eahxi ).

From this, it follows that ' 2 D(eahxi ) for any a > 0 as well, sin
e for any Æ > 0,

j

Z

IR

n

=

Z

IR

n

e2ahxi

j'(x)j2 dx

e2ahxi

j (V (x) E ) '(x) j2 dx

k (V E )2 e

<

Æhi

j

k1 k e(a+Æ=2)hi '() k2

1:

**Finally, Lemma 3.4 below shows that r' 2 D(eahxi ). To apply this Lemma in our
**

situation, we let p(x) = eahxi and note that for any a > 0,

(reahxi )=eahxi = arhxi =

ax=hxi

**is uniformly bounded.
**

Lemma 3.4 requires some notation. Letting p(x) be a positive weight fun
tion, we introdu
e the spa
e

F2

w

=

f

:

kf k2 2

Fw

=

Z

Rn

jf (x)j2 + jf (x)j2

p(x) dx <

1 :

**We write kf k2w = RR jf (x)j2 p(x) dx, for any f 2 L2 (Rn ; p(x)dx), and kf k2 = RR jf (x)j2 dx
**

when the weight is one.

n

n

**Let p 2 C 1 be positive, and assume that there exists a
onstant C < 1, su
h
**

that j(rp(x))=p(x)j 2 C for all x 2 R n . Then, for any f 2 Fw2

Lemma 3.4

krf kw C kf kw +

p

kf kw kf kw + C 2 kf k2w :

**We present the proof of this te
hni
al lemma in Se
tion 4.
**

We now state and prove the following Corollary to Proposition 3.3:

14

(3.1)

**Assume the hypotheses of Proposition 3.3. Let R() be the resolvent of
**

H = + V for 2= (H ), and let PE be the nite dimensional spe
tral proje
tor of H on

**E . Let r(E ) = (H E )j(I PE)L 1 be the redu
ed resolvent at E . Then, eahxi R() e ahxi
**

and eahxi r(E ) e ahxi are bounded on L2 (IRn ).

Corollary 3.5

2

**We use the notation of the proof of Proposition 3.3. We know that R () is
ompa
t
**

and analyti
in 2 C , if 62 (H ). Hen
e, for any 1 ; 2 2 C01, the map from IR (H )

to CI given by

(a; ) 7! h 1 ; eav R0 () e av 2 i

is uniformly bounded by C k 1k k 2k on any given
ompa
t set of IR (H ) for some C .

From this we infer that for any a > 0, eahxi R() e ahxi is bounded in L2 (IRn), uniformly for

in
ompa
t sets of (H ). Sin
e the redu
ed resolvent r(E )
an be represented as

Z

1

1 d;

r (E ) =

(3.2)

R0 ()

2i CE

E

where CE is a loop in the resolvent set en
ir
ling only E , the boundedness of eahxi r(E ) e ahxi

follows.

Proof

**To show that the terms of our formal expansion all belong to L2 , we use the following
**

generalization of Proposition 3.3. We present its proof in Se
tion 4.

Assume the hypotheses of Proposition 3.3 and let ' be an L2 solution of

( + V E ) ' = 0. Then, for any a > 0, and any multi-index 2 N n , D' 2 D(eahxi ),

where D = x x xnn .

Proposition 3.6

1

1

2

2

**Exponential de
ay of eigenfun
tions is a well known and well studied property
**

for S
hrodinger operators. (See e.g., the review [6℄.) However, we were unable to nd any

referen
es dealing with the exponential de
ay of all su
essive derivatives of eigenfun
tions

in our framework.

Remark

We now prove that our formal expansion leads to rigorous quasimodes for the Hamiltonian H1() given by (2.1). Theorem 3.7 summarizes this result for the leading order, while

Theorem 3.8 handles the arbitrary order results.

15

**Let h(; W; Z ) be dened as in Se
tion 2 with W shifted so that W0 = 0. We
**

assume h(; W; Z ) on Hel is C 2 in the strong resolvent sense for (W; Z ) near the origin.

We assume its non-degenerate ground state is given by

Theorem 3.7

E1 (; W; Z )

=

+ a1 W 2 + a2 a3 W Z 2 + a4 Z 4 + S (; W; Z )

E0 + E~ (; W; Z ) + S (; W; Z );

E0

(3.3)

**under hypothesis (2.3) or (2.4), and we denote the
orresponding normalized eigenstate by
**

(W; Z ). Suppose the remainder term S is uniformly bounded below by some r > 1 and

that jS j satises a bound of the form

j S (; W; Z ) j C

X

+ 3

(3.4)

j W Z 2 j

**for (W; Z ) in a neighborhood of the origin. Here C is independent of , the sum is nite, and
**

and are non-negative integers. Let f0 (w; z ) be a normalized non-degenerate eigenve
tor

of HNF , i.e.,

( w2 =2 z2 =2 + ENF (w; z)) f0 = E2 f0 ;

with

ENF (w; z ) = a1

+

+ a4 z4 :

Then, for small enough , there exists an eigenvalue E () of H1 () whi
h satises

w2

a2

a3 w z 2

E () = E0 + 2 E2 + O( );

for some > 2 as ! 0.

**At this level of approximation, it is not ne
essary to require the eigenve
tor
**

to satisfy
ondition (2.11) or to require h(; W; Z ) be real symmetri
.

We have stated our results for the ele
troni
ground state, but the analogous results

would be true for any non-degenerate state that had the same type of dependen
e on .

Remarks

1.

2.

**In the
ourse of the proof, we denote all generi
non-negative
onstants by the same
**

symbol
.

Our
andidate for the
onstru
tion of a quasimode is

Q(; W; Z ) = F (W=Æ ) F (Z=Æ ) f0(W=; Z=p) (W; Z );

(3.5)

Proof:

1

2

16

**where F : IR ! [0; 1℄ is a smooth, even
uto fun
tion supported on [ 2; 2℄ whi
h is equal to
**

1 on [ 1; 1℄. One should expe
t the introdu
tion of these
utos not to ae
t the expansion

at any nite order be
ause the eigenve
tors of H1() are lo
alized near the minimum of

E1 (; W; Z ). Thus, the properties of the ele
troni
Hamiltonian for large values (W; Z )

should not matter. The
hoi
e of a dierent
uto for ea
h variable is required be
ause

these variables have dierent s
alings in . We determine the pre
ise values of the positive

exponents Æ1 and Æ2 in the
ourse of the proof. We also use the notation

F (; W; Z ) = F (W=Æ ) F (Z=Æ ):

1

(3.6)

2

**We rst estimate the norm of Q.
**

k Q

k2

=

=

Z

Z

IR2

IR2

jF (; W; Z ) f0(W=; Z=p)j2 k(W; Z )k2Hel

jf0(W=; Z=p)j2 dW dZ

Z

IR2

(1 F 2(; W; Z )) jf0(W=; Z=p)j2 dW dZ:

**The rst term of the last expression equals 3=2 , by s
aling, sin
e f0 is normalized. If Æ1 < 1
**

and Æ2 < 1=2, the negative of the se
ond term is bounded above by

Z

jf (W=; Z=p)j2 dW dZ

jW jÆ1

jZ jÆ2

=

0

3=2

Z

3=2 e

=

jwj1 Æ1

jzj1=2 Æ2

2a(1=(1

Æ1 )

**e 2a(jwj+jzj) e2a(jwj+jzj) jf0 (w; z )j2 dw dz
**

+1=(1

Æ2 )

)

kea(jj+jj)f0k2

O(1);

**sin
e f0 2 D(eah(W;Z )i ). Hen
e,
**

k Qk = 3=4 (1 + O(1)); where the O(1)
orre
tion is non-positive.

(3.7)

Next we
ompute

(H1() (E0 + 2 E2)) Q(; W; Z )

= S (; W; Z ) f0(w; z)jW;Z F (; W; Z ) (W; Z )

17

(3.8)

4

F (; W; Z ) (W; Z ) f0(w; z)jW;Z ;

2

(w f0(w; z)jW;Z ) W (F (; W; Z )(W; Z ))

2

3

3 2

+

Z

W

2

5=2 (z f0 (w; z )jW;Z ) Z (F (; W; Z )(W; Z ));

**where we have introdu
ed the shorthand f0 (w; z)jW;Z = f0 (W=; Z=p) and used the identity
**

p

E~ (; W; Z )

2 ENF (W=; Z= ) 0:

Also

1 F 0(W=Æ ) F (Z=Æ )

F (; W; Z ) =

W

Æ

1

2

1

Z F (; W; Z )

= 1Æ F (W=Æ ) F 0(Z=Æ )

1

2

2

**and, by assumption, kW Z (W; Z )kHel is
ontinuous and of order 0 in a neigborhood of
**

the origin, for + 2. Therefore,

sup k W (F (; W; Z )(W; Z )) kHel

IR2

sup k Z (F (; W; Z )(W; Z )) kHel

IR2

sup k W2 (F (; W; Z )(W; Z )) kHel

IR2

sup k Z2 (F (; W; Z )(W; Z )) kHel

IR2

Æ

Æ

2

Æ

;

2

Æ

1

(3.9)

2

1

2

**where all ve
tors are supported in f (W; Z ) : jW j 2=Æ ; jZ j 2=Æ g. Ea
h of these ve
tors
**

appears in (3.8), multiplied by one of the s
alar fun
tions f0 (w; z)jW;Z , (w f0(w; z)) jW;Z , or

(z f0 (w; z)) jW;Z . In turn, ea
h of these fun
tions belongs to L2 (IR2 ) by Proposition 3.3, and

ea
h one has norm of order 3=4 be
ause of s
aling, e.g.,

Z

1=2

p

2

j ( f )(W=; Z= ) j dW dZ

= 3=4 k f k :

1

IR2

w 0

2

w 0 L2 (IR2 )

**Therefore, the norms of the last three ve
tors in (3.8) are of order 3=4 times the
orresponding
**

power of stemming from (3.9).

18

We now estimate the norm of the term that arises from the error term S . From our

hypothesis on the behavior of S , we have

Z

2

kS F f k =

jf (W=; Z=p) S (W; Z )j2 dW dZ

0

jW j2=Æ1

jZ j2=Æ2

=

X

0

Z

jW j

jZ j

+ 3

X

+ 3

X

Z

2(Æ1 +2Æ2 )

IR2

jf0(W=; Z=p)j2 dW dZ

2(Æ +2Æ ) 3=2 ;

1

+ 3

jf0(W=; Z=p)j2 W Z 2 2 dW dZ

2=Æ1

2=Æ2

2

**where the sums are nite.
**

Colle
ting these estimates and inserting the allowed values of and , we obtain

k (H1() (E0 + 2 E2)) Q k

3=4 3Æ + 2(Æ +Æ ) + Æ +4Æ + 6Æ + 4

1

1

2

1

2

2

2Æ1

+ 3

2Æ 2

+ 3 Æ + 5=2

1

Æ2 :

**We further note that Æ1 < 1 and Æ2 < 1=2 imply 4 2Æ 3 Æ and 3 2Æ 5=2 Æ . This,
**

together with (3.7), shows that for small enough ,

k (H1() (E0 + 2 E2)) Q k
3Æ + 2(Æ +Æ ) + Æ +4Æ + 6Æ + 3 Æ + 5=2 Æ

k Q k

We still must show that all terms in the parenthesis above
an be made asymptoti
ally

smaller than 2 . This
an be done if there exist
hoi
es of Æ1 and Æ2 su
h that all exponents

in the parenthesis above are stri
tly larger than 2. The inequalities to be satised are

1

1

0 < Æ1 < 1;

Æ1 > 2=3; Æ1 + Æ2 > 1;

1

2

0 < Æ 2 < 1=2;

1

1

2

2

2

2

1

2

Æ2 > 1=3; Æ1 + 4Æ2 > 2:

**Satisfying these is equivalent to satisfying
**

(

2=3 < Æ1 < 1

1=3 < Æ2 < 1=2

whi
h denes the set of allowed values. The best value,

=

max min f 3Æ1; 2(Æ1 + Æ2 ); Æ1 + 4Æ2 ; 6Æ2 ; 3

0<Æ1 <1

0<Æ2 <1=2

19

Æ1 ; 5=2 Æ2 g

>

0;

**is obtained by straighforward optimization and is given by = 15=7, obtained for 5=7 <
**

Æ1 < 6=7 and Æ2 = 5=14. With su
h a
hoi
e, there exists an eigenvalue E () of H1 () that

satises

E () = E0 + 2 E2() + O( );

with = 2 + 1=7.

We now turn to the
onstru
tion of a
omplete asymptoti
expansion for the energy level

E () of H1 (), as ! 0.

Assume the hypotheses of Theorem 3.7 with the additional
ondition that

h(; W; Z ) on Hel is C 1 in the strong resolvent sense in the variables (; W; Z ). Then the

energy level E () of H1 () admits a
omplete asymptoti
expansion in powers of 1=2 . The

same
on
lusion is true for the
orresponding quasimode eigenve
tor.

Theorem 3.8

**Our
andidate for the quasimode is again the formal expansion (2.9) trun
ated at
**

order N=2 and multiplied by the
uto fun
tion (3.6), i.e.,

N

X

(; W; Z ) = F (; W; Z )

j=2

(W; Z; W=; Z=p):

Proof

Q

j=2

j =0

**We shall determine j=2 and Tj=2 in (2.8) expli
itly, but rst we introdu
e some notation
**

for
ertain Taylor series. Expanding in powers of 1=2 , we write

Tj=2 (W; Z )

=

Tj=2 (w; 1=2 z )

Tj=2 (W; Z ) Tj=2 (0; 0)

Tj=2 (W; Z )

Tj=2 (0; 0)

1=2 Z Tj=2 (0; 0)

+

1

X

k=1

+

W Tj=2 (0; 0)w + Z Tj=2 (0; 0)w2=2

2

j=(k=2 2) (w; z ) k=2 :

**Next, our hypotheses imply that the fun
tion S (; W; Z ) in (3.3)
**

E1 (; W; Z ) = E0 + E~ (; W; ; Z ) + S (; W; Z )

is C 1 in (; W; Z ). Using (3.4), we write

E1 (; w;

1=2 z )

=

E0

+

2 E

NF

20

(w; z) +

1

X

m6

m=2 Sm=2 (w; z ):

+

**Be
ause we have assumed E1 (; W; Z ) is even in Z , Sm=2 (w; z) = 0 when m is odd,
**

but the notation is somewhat simpler if we in
lude these terms.

We use this notation and substitute the formal series (2.9) and (2.10) into the eigenvalue

equation (2.7), with H2 given by (2.8). For orders n=2 with n 4, we nd exa
tly what we

obtained in Se
tion 2. When n 5, we have to solve

Note

[h(; W; Z )

+

E1 (; W; Z )℄

(3.10)

n=2

ENF (w; z ) (n 4)=2 + S6=2 (w; z ) (n 6)=2 + S7=2 (w; z ) (n 7)=2 + + Sn=2 (w; z ) 0

+ (T (W; Z )

n

2

n( ) (w; z ) 0

T n (0; 0)) 0

1

2

2

+ (T (W; Z )

Tn

n 1

2

2

1

2

(0; 0))

1

n( ) (w; z ) 0

2

2

2

2

((1n=2)2)=2 (w; z ) 1=2

1=2

7

2

T

7

2

(0; 0))

n 7

2

6

2

n 7

2

)

n 6

2

)

(w; z)

(w; z)

0

1=2

( ) (w; z ) (n 7)=2

6

2

1

2

+ (T (W; Z ) T (0; 0)) (n 6)=2

1

1 2

2

2

w;z (n 4)=2 Z;z (n 5)=2 W;w (n 6)=2

2

2 Z;Z

= E2 (n 4)=2 + E5=2 (n 5)=2 + + En=2 0 ;

6

2

6

2

(

...

+ (T (W; Z )

(

6

2

(n 6)=2

1 2

2 W;W

(n 8)=2

**with the understanding that the quantities S , T and that appear with indi
es lower than
**

those allowed in their denitions are equal to zero.

We solve (3.10 by indu
tion on n. We assume that

(

Ej=2; j=? 2(W; Z; w; z); Tj=2 (W; Z ) for j n 1;

and

fj=2 (W; Z; w; z )

for j n 5

have already been determined, with fj=k 2(W; Z; w; z) = 0, for j 1.

We proje
t (3.10) into the (W; Z ) dire
tion and the orthogonal dire
tion in the ele
troni
Hilbert spa
e to obtain two equations that must ea
h be solved.

First, we take the s
alar produ
t of (3.10) with (W; Z ) in the ele
troni
Hilbert spa
e

to obtain

ENF (w; z )f(n 4)=2

+ S6=2 (w; z)f(n

6)=2

+ S7=2 (w; z)f(n

21

7)=2

+ + Sn=2(w; z)f0

+ (T (W; Z )

n( ) (w; z )f0

T n (0; 0))f0

n

2

1

2

2

+ (T (W; Z )

Tn

n 1

2

2

1

2

n( ) (w; z )f0

2

2

1

(0; 0))f1=2

2

2

((1n=2)2)=2 (w; z )f1=2

(

6

2

...

+ (T (W; Z )

T

7

2

7

2

(0; 0)) f

(

n 7

2

)

2

)

(w; z)f0

(w; z)f1=2

( ) (w; z ) f(n 7)=2

n 7

6

2

2

1

2

+ (T (W; Z ) T (0; 0)) f(n 6)=2

1 f

2

2

h(W; Z ); W;w

2 w;z (n 4)=2 h(W; Z ); Z;z (n 5)=2 iH

1 h(W; Z ); 2

1 h(W; Z ); 2

(n 6)=2 iH

Z;Z

W;W (n 8)=2 iH

2

2

6

2

n 6

6

2

6

2

el

el

(n 6)=2 iHel

el

= E2 f(n 4)=2 + E5=2 f(n 5)=2 + + En=2 f0:

(3.11)

We further proje
t (3.11) into the f0 dire
tion and the orthogonal dire
tion in L2 (IR2) to

obtain two equations that must ea
h be solved.

We take the s
alar produ
t of (3.11) with f0 in L2 (R 2 ). Using fj=k 2 = 0 for j 1 and

( 21 w;z + ENF (w; z)) f0 = E2 f0 , we obtain

En=2 = T (W; Z ) T (0; 0)

(3.12)

n

n

2

2

n

X

+

j =6

D

h f0; Sj=2 f(j

n

n 7 nX

6 k

X

6)=2 iL2 (R2 )

2

j =1

k=0

2

2

+ h(W; Z ); W;w

(n 6)=2 iH

oE

1

1

2

2

+ 2 h(W; Z ); Z;Z (n 6)=2 iH + 2 h(W; Z ); W;W (n 8)=2 iH L (R ) :

We
an solve this equation for En=2 if the right hand side is independent of (W; Z ). This will

be true, if we
hoose

f0 ;

2

h (W; Z ); Z;z

h f0; j=(n2 (j+k))=2) fk=2 iL (R )

(n 5)=2 iHel

el

el

T (W; Z )

n

2

n

X

=

+

j =6

D

f0 ;

n

h f0; Sj=2 f(j

6)=2 iL2 (R2 )

2

h(W; Z ); Z;z

+

el

n 7 nX

6 k

X

2

h f0; j=(n2 (j+k))=2) fk=2 iL (R )

2

k=0

j =1

2

2

2

(n 5)=2 iHel + h(W; Z ); W;w (n 6)=2 iHel

2

+ 21 h(W; Z ); Z;Z

(n

1

2

6)=2 iH + h(W; Z ); W;W

2

22

el

(n 8)=2 iHel

oE

L2 (R2 )

We then are for ed to take

T n (0; 0):

En=2 =

2

**The rst non-zero Tj=2(W; Z ) is
**

1

T6=2 (W; Z ) = h (W; Z ); Z2 (W; Z ) iH

h f0; S3 f0 iL (IR ) :

(3.13)

2

So,

E3 = h f0; S3 f0 iL (IR ) 21 h (0; 0); (Z2 )(0; 0) iH :

We next equate the
omponents on the two sides of (3.11) that are orthogonal to f0 in

2

L (IR2 ). The resulting equation
an be solved by applying the redu
ed resolvent rNF (E2 ),

whi
h is the inverse of the restri
tion of ( 12 w;z + ENF E2) to the subspa
e orthogonal to

f0 . We thus obtain

" n 5

n

X

X

?

f(n 4)=2 = rNF (E2 )

E(n j)=2 fj=2

(Sj=2(w; z) f(j 6)=2 )?

2

el

2

+

+

n 7 nX

6 k

X

k=0 j =1

2

el

j =1

j =6

(j=(n2 (j+k))=2) (w; z)fk=2)? +

h (W; Z ); Z;z (n 5)=2 i?Hel

2

2

+ h (W; Z ); Z;Z

(n

2

6)=2 iHel

?

n 6

X

j =1

(T(n

j )=2

(0; 0)

2

+ h (W; Z ); W;w

(n

2

+ h (W; Z ); W;W

(n

T(n j )=2 (W; Z ))fj=?2

6)=2 iHel

?

8)=2 iHel

?

#

;

**This solution has f(n 4)=2 = f(?n 4)=2 orthogonal to f0 , as
laimed in Se
tion 2. The rst
**

non-trivial fj=2, for j 1 is

f1?(W; Z; w; z ) = rNF (E2 ) (S3 (w; z ) f0 (w; z ))?:

(3.14)

Next, we equate the
omponents of (3.10) that are orthogonal to (W; Z ) in Hel . We

solve the resulting equation for n=? 2 by applying the redu
ed resolvent r(W; Z ) of h(; W; Z )

at E1 (; W; Z ). This" yields

?

n=2

= r(W; Z )

+

n 5

X

j =1

E(n

?

j )=2

j=2

n 7 nX

6 k

X

j=(n2 (j +k))=2)

k=0 j =1

2

+ (Z;z

2

+ (W;W

(n 5)=2 )

n

X

j =6

Sj=2 (w; z ) (?j 6)=2

n 6

X

(w; z) k=? 2 + (T(n j)=2 (0; 0)

j =1

2 + 2 )

+ ((W;w

Z;Z

?

(n 8)=2 )

?

(3.15)

(n 6)=2 )

?

( 21 w;z + ENF (w; z) E2)

23

?

T(n j )=2 (W; Z )) j=

2

?

(n 4)=2

#

:

**The rst non-zero
omponent j=? 2 with j 0, is
**

?

5=2 (W; Z; w; z ) = (z f0 )(w; z ) r(W; Z ) (Z )(W; Z ):

(3.16)

p

**Finally, Proposition 3.10 below shows that ea
h j=2 in this expansion belongs to D(ea(jW j=+jZ j= )).
**

As a result, whenever a derivative a
ts on the
uto, it yields a
ontribution whose L2 norm

is exponentially small. This way, we
an negle
t su
h terms. For example

( F (; W; Z )) (W; Z; W=; Z=p) = Æ F 0(W=Æ ) F (Z=Æ ) (W; Z; W=; Z=p):

j=2

W

1

1

2

j=2

**The square of the L2 norm of this term is bounded by a
onstant times
**

Z

p

2

Æ

j j=2(W; Z; W=; Z=p)j2e2a(jW j=+jZ j= )e 2a(1= ) dW dZ = O(1):

1

1

Æ1

jW j=Æ1 1;jZ j=Æ2 2

**Thus, we have
onstru
ted the non-zero quasimode (3.5) that satises the eigenvalue
**

equation up to an arbitrary high power of 1=2 .

The proof of Proposition 3.10 relies on the following lemma.

Let V be a polynomial that is bounded below, su
h that the spe
trum of H =

1 + V purely dis
rete. Let ' 2 C 1 (IRn ) satisfy D ' 2 D(eahxi ), for all 2 Nn and any

2

a > 0. If R() denotes the resolvent of H , then D R()' 2 D(eahxi ) for all 2 Nn and all

in (H ). The same is true for D r(E )', where r(E ) is the redu
ed resolvent at E .

Lemma 3.9

We rst note that ellipti
regularity implies that the resolvent R() maps C 1 fun
tions to C 1 fun
tions. Next, applied to smooth fun
tions in L2 , we have the identity

Proof

[ x ; R() ℄ = R() (x V ) R():

j

j

We
laim that the operators on the two sides of this equation have bounded extensions to all

of L2 . To see this, note that D V is relatively bounded with respe
t to V for any 2 n,

be
ause V is a polynomial. Furthermore, sin
e H V , we see that D V is relatively

bounded with respe
t to H , whi
h implies the
laim. Hen
e, for ' as in the lemma, we have

x R() = R() x ' + R() (x V ) R() ':

(3.17)

The rst term on the right hand side of this equation belongs to D(eahxi ) sin
e R() maps

exponentially de
aying fun
tions to exponentially de
aying fun
tions (see Corollary 3.5). The

N

j

j

j

24

**same is true for the se
ond term, with a possible arbitrarily small loss on the exponential
**

de
ay rate, due to the polynomial growth of x V . This provides the starting point for an

indu
tion on the order of the derivative that appears in the
on
lusion of the lemma.

We now assume that for some 2 n, DR(z)' is a linear
ombination of smooth

fun
tions of the form R(z)(D
V )R(z) R(z)(D
V )R(z)D
' all of whi
h belong to

D(eahxi ), for any a > 0. We assume every
that o
urs here has j
j jj. Then x D R(z )'

is a linear
ombination of elements of the form

x (R(z )(D
V )R(z ) R(z )(D
V )R(z )D
')

Applying (3.17) su
essively, we see that the stru
ture is preserved. Sin
e all D
V are

polynomial, Corollary 3.5 implies the result.

The statement for the redu
ed resolvent follows from the representation (3.2).

j

N

j 1

1

j

j

j 1

1

j

j

k

Assume the hyptheses of Theorem 3.8. Let j=2 (W; Z; w; z ) be determined by the
onstru
tion above, where (W; Z ) belongs to a
losed neighborhood

of the origin and (w; z ) 2 IR2 . Then j=2 is C 1 , and the fun
tion G(w; z ) = sup(W;Z )2

j j=2 (W; Z; w; z )j

belongs to D(eah(w;z)i ).

Proposition 3.10

**The hypothesis on the Hamiltonian and the properties of the normal form HNF
**

proven above imply that (W; Z ) and r(W; Z ) are smooth, and that rNF (E2) maps smooth

fun
tions to smooth fun
tions. We also know that the non-degenerate eigenstate f0 is smooth

and belongs to D(eah(w;z)i ). The smoothness of j=2(W; Z; w; z) follows trivially in

IR2 .

Con
erning the exponential de
ay, we observe that the (w; z) dependen
e of j=2 stems

from the su
essive a
tions of derivatives, redu
ed resolvents, and multipli
ations by polynomials in (w; z), a
ting on the eigenstate f0 . Lemma 3.9 applied in
onjun
tion with Proposition 3.6 shows that the exponential de
ay properties are preserved under su
h operations.

Proof

4 Te
hni
alities

In this se
tion, we present the proofs of Lemma 3.4 and Proposition 3.6.

Proof of Lemma 3.4

x 2 R n , and that

We rst note that the hypothesis on p implies p(x) > 0 for any

e 2C jx yj p(x)=p(y ) e2C jx yj :

(4.1)

25

**Let BR 2 R n be a ball of radius R > 0. We rst show that f 2 L2 (BR+1 ) and f 2 L2 (BR+1 )
**

imply f 2 H 2(BR ), where

H 2 (BR ) = f f

2 L2 (BR ); rf 2 L2 (BR ); and f 2 L2(BR ) g:

**We denote the usual H 2(BR ) norm by k kH (B ). We now show the existen
e of a
onstant
**

K (R) > 0, whi
h depends only on R, su
h that

2

Z

BR

jrf j2

K (R )

Z

R

jf j2 + jf j2 :

BR+1

(4.2)

This estimate does not hold in general if the balls over whi
h one integrates have the

same radius.

We set g = f on BR+1 and g(x) = 0 if jxj > R +1. We
an then de
ompose f = f1 + f2

with f1 and f2 solutions to

(

f1 = g;

f1 jB = 0

f2 = 0

jxj R + 1:

Thus, f1 2 H 2(BR+3 ), and there exists a
onstant
1 (R), whi
h depends only on R, su
h

that

Note

R+3

kf1kH (B

2

R+3

so that

1 (R) kf1 kL (B

)

2

krf1kL (B

2

R+1

)

R+3

)

=
1(R) kf kL (B

2

kf1kH (B

2

R+3

)

R+1

(4.3)

);

1 (R) kf kL (B

2

R+1

):

By the mean value property for harmoni
fun
tions, f2 also satises estimate (4.2), for some

onstant K2 (R) with f2 = 0 (see e.g., Chapter 8 of [1℄). Combining these arguments, we

see that for
2 (R) =
1(R) + K2 (R),

Z

jr(f1 + f2

BR

R

BR+1

)j2

2(R)

Z

BR+1

(jf1j2 + jf2j2)

2(R)

Z

BR+1

(jf j2 + 2(jf j2 + jf1j2)):

But

jf1j2 kf1k2H (B ), so (4.3) implies that (4.2) holds for some
onstant K (R).

Be
ause of (4.1), we
an insert the weight p into this estimate to establish the existen
e

of another
onstant K~ (R), whi
h depends only on R, su
h that

Z

Z

2

~

p jrf j K (R)

p (jf j2 + jf j2):

(4.4)

BR

2

R+3

BR+1

**In other words, p1=2 rf 2 L2lo
if f 2 Fw2 .
**

26

**A se
ond step
onsists in showing that p1=2 rf is in L2(R n ) and satises (3.1). Let
**

R 2 C 1 (R n ) be a trun
ation fun
tion su
h that 0 R 1, with R (x) = 1 if jxj R,

and R (x) = 0 if jxj R + 1. We
an take R so that krRk1 is independent of R. Let

f 2 Fw2 , and set fR = R f . Sin
e rfR = R rf + f rR , we see that kp1=2 rfR kL (B ) =

kp1=2 rf kL (B ) , and

lim kp1=2 (fR f )kL (R ) ! 0;

R!1

by Lebesgue dominated
onvergen
e. By the same argument with fR = Rf + f R +

2rR rf ,

lim kp1=2 (f (R f + f R ))kL (R ) = 0:

R!1

We have the estimate kp1=2 rR rf k2L (B )
2 RB nB p1=2 jrf j2, for some
onstant

2 , independent of R. We
an
over the set BR+1 n BR by a nite set of balls fB1 (j )gj =1;;N (R) ,

of radius 1,
entered at points xj su
h that jxj j = R + 1=2. In ea
h of these balls B1(j ), we

an apply (4.4) (with a
onstant K~ 1, independent of R), to see that

2

2

R

R

n

2

2

2

Z

p

BR+1 nBR

jrf j2

R+1

R+1

2 K~ 1

NX

(R) Z

j =1

B2 (j )

n

R

p (jf j2 + jf j2);

**where B2(j ) has radius 2 instead of 1. Using [jN=1(R) B2 (j ) BR+3 n BR 3 , and taking into
**

a
ount that
ertain points are
ounted (uniformly) nitely many times in the integral, we

eventually obtain

kp1=2 r

R

rf k2 2

L (Rn )

3

Z

BR+1 nBR

p (jf j2 + jf j2);

**where
3 is uniform in R. By the dominated
onvergen
e theorem again, this integral goes
**

to zero as R goes to innity. So, we nally obtain

lim kp1=2 (f fR ))kL (R ) = 0:

2

R!1

n

Sin e fR belongs to H 2(Rn ), the set of ompa tly supported fun tions in H 2, we ompute

**r p fR rfR = p fR fR + jrfR j2 p + fR rp rfR :
**

Sin
e fR has
ompa
t support, Stokes Theorem and our hypotheses on rp show that

Z

Z

Z

2

p jfR j = fR fR p +

fR rp rfR

Z

jfR

j2 p

1=2 Z

jfR

1=2

j2 p

27

+ 2C

Z

jfR

1=2 Z

j2 p

jrfR

j2p

1=2

;

**or, in other words,
**

krfRk2p kfR kw kfRkw + 2 C krfRkw kfR kw :

**This estimate implies (3.1) for fR. The right hand side of that estimate has a nite limit as
**

R ! 1 with f in pla
e of fR on the right hand side. Sin
e

Z

Z

2

p jrf j

p jrfR j2 ;

BR

L1 R n

**we dedu
e that p jrf j2 2 ( ) and satises (3.1).
**

Proof of Proposition 3.6

of [14℄:

Let f 2 L2 (IRn ).

We use the following Paley{Wiener theorem, Theorem IX.13

**Then eajxj f 2 L2 (IRn ) for all a < a0 if and only if fb has an analyti
**

ontinuation to the set fp : jIm pj < a0 g with the property that for ea
h t 2 IRn with jtj < a0 ,

fb( + it) 2 L2 (IRn ), and for any a < a0 , supjtja0 kfb( + it)k2 < 1.

**We refer to the
onditions on fb in this theorem as \the Paley{Wiener
onditions."
**

Sin
e eajxj ' 2 L2 (IRn) is equivalent to ' 2 D(eahxi ), Proposition 3.3 shows that 'b is

analyti
everywhere and satises the Paley{Wiener
onditions. The fun
tions p 7! pj 'b(p)

and p 7! Pj p2j 'b(p) also satisfy these
onditions.

As a preliminary remark, we note that for any xed t 2 IRn, there exist K (t) > Ke (t) > 0

and R(t) > 0, su
h that if p 2 IRn satises Pj p2j R(t), then

Ke (t)

n

X

j =1

p2j

n

X

j =1

itj 2

(pj + ) K (t)

n

X

j =1

p2j :

(4.5)

**So, if BR is a ball of radius R with
enter at the origin, d' satises
**

Z

n

X

IR nBR(t)

n

j =1

p2j

!2

j'^(p + it)j2 dp < 1;

(4.6)

**uniformly for t in
ompa
t sets of IRn.
**

We now start an indu
tion on the length jj of the multi-index in D'. We rst

show that p 7! pj pk 'b(p) satises the Paley{Wiener
onditions for any j; k 2 f1; ; ng.

Note that we only need to prove estimates for large values of the jpj j's. Also, note that if

Pn

2

j =1 pj R(t) > 1, there exists a
onstant C (t) > 0 su
h that

j (pj + itj ) (pk + itk ) j C (t)

n

X

j =0

(4.7)

p2j ;

28

**Therefore, (4.6) implies that
**

Z

j (pj + itj ) (pk + itk ) j2 j'b(p + it)j2 dp

IR nBR(t)

Z

n

C 2 (t)

< 1;

n

X

IR nBR(t)

n

j =1

p2j

!2

j'b(p + it)j2 dp

**uniformly for t in
ompa
t sets of IRn. Hen
e, x x ' 2 D(eahxi ) for any a > 0.
**

We next turn to third order derivatives. Consider the derivative of ' +(V E )' = 0.

For any j 2 f 1; ; ng,

j

xj '

k

= (x V )' + (V E ) x ':

j

j

**Sin
e V is a polynomial, Proposition (3.3) shows that x ' 2 D(eahxi ), for any a > 0.
**

Thus, the fun
tion p 7! pj (Pnj=0 p2j ) 'b(p) satises the Paley{Wiener
onditions.

Consider now any triple of indi
es j; k; l. For Pnj=0 p2j R(t), we have

j

j (pj + itj ) (pk + itk ) (pl + itl ) j C (t) jpj + itj j

n

X

j =0

p2j :

**Hen
e, using this estimate with (4.6), we dedu
e that
**

Z

j (pj + itj ) (pk + itk ) (pl + itl ) j2 j'b(p + it)j2 dp

IR nBR(t)

Z

n

C 2 (t)

< 1;

IR nBR(t)

n

jpj + itj j2

n

X

j =1

p2j

!2

j'b(p + it)j2 dp

**uniformly for t in
ompa
t sets of IRn. Therefore, the Paley{Wiener Theorem asserts that
**

x x x ' 2 D(eahxi ), for any a > 0.

We now pro
eed by assuming D ' 2 D(eahxi ), for any a > 0 and any , su
h that

j j m. Let have jj = m + 1. Let ~ be any multi-index of length m 1. Dierentiating

the eigenvalue equation again, Leibniz's formula yields

j

k

l

D~ '

=

X

0 ~

C ~ D~

(V E ) D ';

(4.8)

**where the C
~ are multinomial
oeÆ
ients. The indu
tion hypothesis and the assumption
**

that V is a polynomial show that D~ ' 2 L2 (IRn). Therefore, p 7! p~ (Pnj=1 p2j ) 'b(p)

29

**satises the Paley{Wiener
onditions. In , there are two indi
es, j and k , not ne
essarily
**

distin
t, whi
h are larger or equal to one, su
h that we
an write

(p + it)

(4.9)

= (p1 + it1 ) (pj + itj ) 1 (pk + itk ) 1 (pn + itn ) (pj + itj ) (pk + itk ):

Estimating the absolute value of the last two fa
tors by (4.7) and using that

~ = (1 ; ; j 1; ; k 1; ; n ) has length m 1, we see that p 7! p 'b(p) satises

the Paley{Wiener
onditions. Hen
e, D ' 2 D(eahxi ) for any a > 0.

1

j

n

k

Referen
es

[1℄ Axler, S., Bourdon, P., and Ramey, W.: Harmoni
Fun
tion Theory, 2nd edition,

New York, Springer, 2001.

[2℄ Elghobashi, N. and Gonzalez, L.: A Theoreti
al Anharmoni
Study of the Infrared

Absorption Spe
tra of F HF , F DF , OHF , and ODF Ions. J. Chem. Phys.

, arti
le 174308 (2006).

124

[3℄ Hagedorn, G.A.: High Order Corre
tions to the Time-Independent BornOppenheimer Approximation I: Smooth Potentials. Ann. Inst. H. Poin
are Se
t.

A. , 1{16 (1987).

47

**[4℄ Hagedorn, G.A. and Joye, A.: A Mathemati
al Theory for Vibrational Levels
**

Asso
iated with Hydrogen Bonds II: The Non{Symmetri
Case. (in preparation).

[5℄ Hagedorn, G.A. and Toloza, J.H.: Exponentially A
urate Quasimodes for the

Time{Independent Born{Oppenheimer Approximation on a One{Dimensional

Mole
ular System. Int. J. Quantum Chem. , 463{477 (2005).

105

[6℄ Hislop, P.: Exponential de
ay of two-body eigenfun
tions: A review, In Mathemati
al Physi
s and Quantum Field Theory, Ele
tron. J. Di. Eqns., Conf. ,

265{288 (2000).

4

**[7℄ Hislop, P. and Sigal, M.: Introdu
tion to Spe
tral Theory with Appli
ations to
**

S
hrodinger Operators, Applied Mathemati
s S
ien
es, Volume

, New York,

Springer, 1996.

113

30

**[8℄ Hormander, L.: Linear Partial Dierential Operators, Berlin, Gottingen, Heidelberg, Springer, 1964.
**

[9℄ Heler, B. and Nourrigat, J.:

Hypoellipti ite maximale pour des operateurs

polyn^omes de hamps de ve teurs, Boston, Birkhaser, 1985.

[10℄ Kato, T.:

Perturbation Theory for Linear Operators, New York, Springer, 1980.

**[11℄ Kawagu
hi, K. and Hirota, E.: Diode Laser Spe
tros
opy of the 3 and 2 Bands
**

of F HF in 1300
m 1 Region. J. Chem. Phys. , 6838{6841 (1987).

87

[12℄ Mohamed, A. and Nourrigat, J.:

**En
adrement du N () pour un operateur de
**

S
hrodinger ave
un
hamp magnetique et un potentiel ele
trique, J. Math. Pures

Appl. 70, 87{99 (1990).

**[13℄ Reed, M. and Simon, B.: Methods of Modern Mathemati
al Physi
s I. Fun
tional
**

Analysis, New York, London, A
ademi
Press, 1972.

[14℄ Reed, M. and Simon, B.:

Methods of Modern Mathemati al Physi s II. Fourier

Analysis, Self-Adjointness, New York, London, A ademi Press, 1975.

**[15℄ Reed, M. and Simon, B.: Methods of Modern Mathemati
al Physi
s IV. Analysis
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of Operators, New York, London, A
ademi
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