A Mathemati al Theory for Vibrational Levels

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 di erently
from those of the heavier nu lei, and we employ a spe ialized form for the ele tron energy level surfa e. Consequently, anharmoni e e 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 di erent. The mathemati al analysis of that situation
is onsequently ompletely di erent.
The model we present here di ers 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 de ne  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 di erent 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 e e 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 Hel er 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 de ned
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 de ne 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 in nity as k (w; z) k ! 1. When (2.4) is
satis ed 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 satis ed 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 e e 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. Di erent 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 uto s 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 satis es
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 )

= f k(W; Z; w; z) +

f ?(W; Z; w; z )

where for ea h xed W and Z , f k(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 f k(W; Z; ;  ) has no (W; Z ) dependen e. We will not pre isely
normalize our approximate eigenfun tions, so we hen eforth assume f k (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 uto s and proving that many te hni al onditions are satis ed 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

De ne

mV (x)

X

jD V (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 de ned 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 ( ) = ei v 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, de ned 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 satis es
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 ( )', de ned 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    x nn .
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 de ned 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 satis es 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 satis es
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 uto s not to a e 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 di erent uto for ea h variable is required be ause
these variables have di erent 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 +2 Æ2 )

IR2

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

2( Æ +2 Æ ) 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 satis ed 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 de nes 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
satis es
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 de nitions 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 satis es 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, D R(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  j j. 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 satis es 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 satis es (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 in nity. 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 satis es (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 satis es 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 satis es 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' satis es
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 j j of the multi-index in D '. We rst
show that p 7! pj pk 'b(p) satis es 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) satis es 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 j j = m + 1. Let ~ be any multi-index of length m 1. Di erentiating
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

satis es 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) satis es
the Paley{Wiener onditions. Hen e, D ' 2 D(eahxi ) for any a > 0.
1

j

n

k

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31