Professional Documents
Culture Documents
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 ap-
proximation that is spe
i
ally designed to des
ribe mole
ules with symmetri
al Hy-
drogen 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 en-
ergy 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.
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 approxima-
tion. 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 in-
volved 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.
A
knowledgements The authors would like to thank Thierry Gallay for several help-
ful
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.
3
In these Ja
obi
oordinates, it has the form
1 mAB
M
2M R
2 mA mB W
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 3
W
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 3 2
H1 () =
2 W 2 2 Z 2 + h(; W; Z ): (2.1)
The ele
tron Hamiltonian h(; W; Z ) is an operator in the ele
troni
Hilbert spa
e that de-
pends 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 + a2 a3 (W 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 + a2 a3 (W W0 ) Z 2 + a4 Z 4 ;
is bounded below, we assume that either
a23 < 4 a1 a4 ; (2.3)
or
a23 = 4 a1 a4 and a2 0: (2.4)
These
onditions are equivalent to the property Ee1(; W; Z ) C for some C , sin
e we
an write
a3 2 2 a23
Ee1 (; W; Z ) = a1 (W W0 )
2a1 Z + a4
4a1 Z4 + a2 Z 2 :
By res
aling with w = (W W0 )= and z = Z=1=2 , we see that the Hamiltonian
4 2 3 2
2 W 2 2 Z 2 + Ee1 (; W; Z )
5
is unitarily equivalent to 2 times the {independent Normal Form Hamiltonian
HNF =
1 2 1 2
2 w2 2 z2 + ENF(w; z); (2.5)
where
ENF (w; z ) = a1 w2 + a2 a3 w z 2 + a4 z 4 : (2.6)
Remark 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 2 1 2
HNF '
2 s2 2 t2 + 1 s + 2 t 3 s t + t ;
2 2 2 2 4
with
a a a
= a4 1=6 ; 1 = 2=13 ; 2 = 22=3 ; and 3 = 53=6 :
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.
Expli
it Computations for FHF The expression (2.2) is
learly spe
ial. Our
ompu-
tations 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
6
data was numeri
ally quite unstable, and that
ondition (2.3) was barely satised by these
aj .
0.4
0.3
Displacement of H from F − F Center of Mass
0.2
0.1
−0.1
−0.2
−0.3
−0.4
2.1 2.2 2.3 2.4 2.5
F − F Distance
Figure 1. 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.
The experimentally observed values [11℄ for the ex
itation energies to the rst symmet-
ri
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 pre-
di
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 eigen-
value 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.
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 .
Note: 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.
Order 0 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 as-
sumptions, 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;
el (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 1 2= The order 1=2 terms require
[ h(; W; Z ) E (; W; Z ) ℄ 1=2 + E0 1=2 = E0 1=2 + E1=2 0:
9
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 ) E (; W; Z ) ℄ 1=2 = 0;
so
1=2 (W; Z; w; z ) = f1=2 (W; Z; w; z ) (W; Z ):
Orders 1 and 3 2 = 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 ); and
3=2 (W; Z; w; z ) = f3=2 (W; Z; w; z ) (W; Z ):
Order 2 The order 2 terms that are multiples of (W; Z ) in the ele
troni
Hilbert spa
e
require
1 2 f0 (W; Z; w; z) 1 2 f0
(W; Z; w; z) + ENF (w; z ) f0 (W; Z; w; z )
2 w2 2 z 2
= E2 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 ):
2
We split the s
alar fun
tions f (W; Z; w; z) with > 0 into two
ontributions
f (W; Z; w; z ) = fk(W; Z; w; z) + f?(W; Z; w; z )
+ ?
m=2 (W; Z; w; z);
where m=? is obtained by applying the redu
ed resolvent operator [ h(; W; Z )
2 E (; W; Z ) ℄r 1
to the right hand side of the equation.
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.
Proposition 3.1 Assume (2.3) or (2.4).
Then, the spe
trum of HNF =
1 2 1 2 + ENF (w; z ) is purely dis
rete.
2 w2 2 z2
This proposition is an easy
onsequen
e of the following general
riterion [12℄ that guar-
antees 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℄.)
Proposition 3.2 ([12℄, Thm 1.3) Let V (x) 0 be a non-negative polynomial in x 2 IRn .
Dene
X
mV (x) =1+ jDV (x)j;
2Nn
where =
D
x1 x2
1 2
xn , and the sum is nite. Let H
n = + V be self-adjoint on a
domain in ( )
L2 R n . Then the resolvent of H is
ompa
t if and only if limjxj!1 mV (x) = 1.
Proof of Prop. 3.1 One easily
he
ks that limjxj!1 mENF (x) = 1, so Prop. 3.1 is an
immediate
onsequen
e of Prop. 3.2.
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.
Proposition 3.3 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,
' 2 D(eahxi ); r' 2 D(eahxi ); and ' 2 D(eahxi );
v
u n
u X
where hxi = t 1+ x2j , and D(eahxi ) denotes the domain of multipli
ation by eahxi .
j =1
12
Proof 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
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 j j
Z
= e2ahxi j (V (x) E ) '(x) j2 dx
IR
n
is uniformly bounded.
Lemma 3.4 requires some notation. Letting p(x) be a positive weight fun
tion, we intro-
du
e the spa
e
Z
F2 w = f : kf k2 2
Fw = jf (x)j2 + jf (x)j2 p(x) dx < 1 :
Rn
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
n n
14
Corollary 3.5 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
2
Proof 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
r (E ) =
1 R0 ()
1 d; (3.2)
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.
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.
Proposition 3.6 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 .
1
1
2
2
Remark 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.
We now prove that our formal expansion leads to rigorous quasimodes for the Hamilto-
nian 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
Theorem 3.7 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
E1 (; W; Z ) = + a1 W 2 + a2 a3 W Z 2 + a4 Z 4 + S (; W; Z )
E0
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 w2 + a2+ a4 z4 :
a3 w z 2
Then, for small enough , there exists an eigenvalue E () of H1 () whi
h satises
E () = E0 + 2 E2 + O( );
for some > 2 as ! 0.
Remarks 1. 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
.
2. 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 .
Proof: 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 );
1 2
(3.5)
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 2
(3.6)
We rst estimate the norm of Q.
Z
k Q k2 = jF (; W; Z ) f0(W=; Z=p)j2 k(W; Z )k2Hel
IR2
Z
= jf0(W=; Z=p)j2 dW dZ
IR2
Z
(1 F 2(; W; Z )) jf0(W=; Z=p)j2 dW dZ:
IR2
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 0
jZ jÆ2
Z
= 3=2 jwj1 Æ1 e 2a(jwj+jzj) e2a(jwj+jzj) jf0 (w; z )j2 dw dz
jzj1=2 Æ2
where we have introdu
ed the shorthand f0 (w; z)jW;Z = f0 (W=; Z=p) and used the iden-
tity
E~ (; W; Z )
p
2 ENF (W=; Z= ) 0:
Also
F (; W; Z ) =
1 F 0(W=Æ ) F (Z=Æ )
1 2
W
Æ
1
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 Æ
IR2 1
sup k Z (F (; W; Z )(W; Z )) kHel Æ
(3.9)
IR2 2
sup k W2 (F (; W; Z )(W; Z )) kHel 2
Æ
IR2 1
sup k Z2 (F (; W; Z )(W; Z )) kHel 2
Æ
;
IR2 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
1 2
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
j ( f )(W=; Z= ) j dW dZ
2 = 3=4 k f k :
w 0 w 0 L2 (IR2 )
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
kS F f k =
0
2 jf (W=; Z=p) S (W; Z )j2 dW dZ
jW j2=Æ1 0
jZ j2=Æ2
Z
jf0(W=; Z=p)j2 W Z 2 2 dW dZ
X
jW j 2=Æ1
+ 3 jZ j2=Æ2
Z
jf0(W=; Z=p)j2 dW dZ
X
2(Æ1 +2Æ2 )
+ 3 IR2
X
=
2(Æ +2Æ ) 3=2 ;
1 2
+ 3
We further note that Æ1 < 1 and Æ2 < 1=2 imply 4 2Æ 3 Æ and 3 2Æ 5=2 Æ . This, 1 1 2 2
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
0 < Æ1 < 1; Æ1 > 2=3; Æ1 + Æ2 > 1; 0 < Æ 2 < 1=2; Æ2 > 1=3; Æ1 + 4Æ2 > 2:
19
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.
Theorem 3.8 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.
Proof 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.,
(W; Z; W=; Z=p):
XN
(; W; Z ) = F (; W; Z )
Q j=2 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) 1=2 Z Tj=2 (0; 0) + W Tj=2 (0; 0)w + Z Tj=2 (0; 0)w2=2
2 +
1
X
Tj=2 (W; Z ) Tj=2 (0; 0) + j=(k=2 2) (w; z ) k=2 :
k=1
Next, our hypotheses imply that the fun
tion S (; W; Z ) in (3.3)
E1 (; W; Z ) = E0 + E~ (; W; ; Z ) + S (; W; Z )
20
Note 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
[h(; W; Z ) E1 (; W; Z )℄ n=2 (3.10)
+ 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
...
1 2 2 1 2 1 2
w;z (n 4)=2 Z;z (n 5)=2 W;w (n 6)=2
2 2 Z;Z (n 6)=2
2 W;W (n 8)=2
...
1 f
2 w;z (n 4)=2 h(W; Z ); Z;z (n 5)=2 iH h(W; Z ); W;w (n 6)=2 iHel
2 2
el
1 h(W; Z ); 2 1 h(W; Z ); 2
(n 6)=2 iH W;W (n 8)=2 iH
2 Z;Z 2 el el
j =6 k=0 j =1
D n
f0 ; h (W; Z ); Z;z
2+ h(W; Z ); W;w
2
(n 5)=2 iHel
(n 6)=2 iH el
1 1 oE
+ 2 h(W; Z ); Z;Z (n 6)=2 iH + 2 h(W; Z ); W;W (n 8)=2 iH L (R ) :
2 2
el el 2 2
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
n
X n 7 nX
X 6 k
T (W; Z )
n
2
= h f0; Sj=2 f(j 6)=2 iL2 (R2 ) + h f0; j=(n2 (j+k))=2) fk=2 iL (R ) 2 2
j =6 k=0 j =1
D n
+ f0 ; h(W; Z ); Z;z
2
(n 5)=2 iHel + h(W; Z ); W;w (n 6)=2 iHel
2
+ 21 h(W; Z ); Z;Z 1 oE
6)=2 iH + h(W; Z ); W;W (n 8)=2 iHel
2 2
(n
2
el
L2 (R2 )
22
We then are for
ed to take
En=2 = T n (0; 0):
2
So,
E3 = h f0; S3 f0 iL (IR ) 21 h (0; 0); (Z2 )(0; 0) iH :
2 2
el
We next equate the
omponents on the two sides of (3.11) that are orthogonal to f0 in
L (IR2 ). The resulting equation
an be solved by applying the redu
ed resolvent rNF (E2 ),
2
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 )?
j =1 j =6
n 7 nX
X 6 k n 6
X
+ (j=(n2 (j+k))=2) (w; z)fk=2)? + (T(n j )=2 (0; 0) T(n j )=2 (W; Z ))fj=?2
k=0 j =1 j =1
+ h (W; Z ); Z;z (n 5)=2 i?Hel
2 + h (W; Z ); W;w
2
(n 6)=2 iHel
?
#
+ h (W; Z ); Z;Z
2
(n 6)=2 iHel
? + h (W; Z ); W;W
2
(n 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 5
X n
X
?
n=2 = r(W; Z ) E(n j )=2
?
j=2 Sj=2 (w; z ) (?j 6)=2 (3.15)
j =1 j =6
n 7 nX
X 6 k X n 6
+ j=(n2 (j +k))=2) (w; z) k=? 2 + (T(n j)=2 (0; 0) T(n j )=2 (W; Z )) j=
?
2
k=0 j =1 j =1
+ (Z;z
2
(n 5)=2 )
? + ((W;w
2 + 2 )
Z;Z (n 6)=2 )
?
#
+ (W;W
2
(n 8)=2 )
? ( 21 w;z + ENF (w; z) E2) ?
(n 4)=2 :
23
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):
W j=2
1 1 2
j=2
Proof 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
[ 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, N
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
N
fun
tions of the form R(z)(D
V )R(z) R(z)(D
V )R(z)D
' all of whi
h belong to
1 j 1 j
D(eahxi ), for any a > 0. We assume every
that o
urs here has j
j jj. Then x D R(z )'
j
Applying (3.17) su essively, we see that the stru ture is preserved. Sin e all D V are k
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 We rst note that the hypothesis on p implies p(x) > 0 for any
x 2 R n , and that
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
2
R
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
kf1kH (B 2
R+3 )
1 (R) kf1 kL (B 2
R+3 ) =
1(R) kf kL (B 2
R+1 ); (4.3)
so that
krf1kL (B
2
R+1 ) kf1kH (B 2
R+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 Z Z
jr(f1 + f2 )j2
2(R) (jf1j2 + jf2j2)
2(R) (jf j2 + 2(jf j2 + jf1j2)):
BR BR+1 BR+1
R
But BR+1 jf1j2 kf1k2H (B ), so (4.3) implies that (4.2) holds for some
onstant K (R).
2
R+3
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 BR+1
kp1=2 rf kL (B ) , and
2
R
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
2 n
We have the estimate kp1=2 rR rf k2L (B )
2 RB nB p1=2 jrf j2, for some
onstant
2
R+1 R+1 R
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
Z (R) Z
NX
p jrf j2
2 K~ 1 p (jf j2 + jf j2);
BR+1 nBR j =1 B2 (j )
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
Z
kp1=2 r R rf k2 2
L (Rn )
3 p (jf j2 + jf j2);
BR+1 nBR
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
R!1
lim kp1=2 (f fR ))kL (R ) = 0: 2 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
p jfR j = fR fR p + fR rp rfR
2
27
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
p jrf j
2 p jrfR j2 ;
BR
we dedu
e that p jrf j2 2 ( ) and satises (3.1).
L1 R n
Proof of Proposition 3.6 We use the following Paley{Wiener theorem, Theorem IX.13
of [14℄:
Let f 2 L2 (IRn ). 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
n
X X n n
X
Ke (t) p2j
(pj + ) K (t)
itj 2 p2j : (4.5)
j =1 j =1 j =1
28
Therefore, (4.6) implies that
Z
j (pj + itj ) (pk + itk ) j2 j'b(p + it)j2 dp
IR nBR(t)
n
Z !2
n
X
C 2 (t) p2j j'b(p + it)j2 dp
IR nBR(t)
n
j =1
< 1;
uniformly for t in
ompa
t sets of IRn. Hen
e, x x ' 2 D(eahxi ) for any a > 0.
j k
We next turn to third order derivatives. Consider the derivative of ' +(V E )' = 0.
For any j 2 f 1; ; ng,
xj ' = (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. j
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
n
X
j (pj + itj ) (pk + itk ) (pl + itl ) j C (t) jpj + itj j p2j :
j =0
Z n
!2
X
C 2 (t) jpj + itj j2 p2j j'b(p + it)j2 dp
IR nBR(t)
n
j =1
< 1;
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.
j k l
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
X
D~ ' = C
~ D~
(V E ) D
'; (4.8)
0
~
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 ):
1 j k n
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.
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.
124, arti
le 174308 (2006).
[3℄ Hagedorn, G.A.: High Order Corre
tions to the Time-Independent Born-
Oppenheimer 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
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