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Molecular spectra, Fermi resonances, and classical motion

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 Molecular spectra, Fermi resonances, and classical motion a)
Eric J. Heller,b) Ellen B. Stechel, and Michael J. Davis
Department of Chemistry, University of California, Los Angeles, California 90024
(Received 8 January 1980; accepted II April 1980)

Classically periodic molecular vibration (such as a totally symmetric stretch) can be unstable against the
addition of small components of other modes, depending on anharmonic coupling strengths, near
resonance of fundamental frequencies, and the total energy. We report here on some very strong
correspondances between classical stability of the motion and quantum spectral features, wave functions,
and energy transfer. The usual concept of a vibrational Fermi resonance turns out to apply best to the
case where the transition to classical instability occurs at an energy below the first resonant quantum
levels (this is the case for the famous Fermi resonance in CO 2), In the (probably more common) event
that resonant classical instability should set in above several quanta of energy in the mode of interest, the
quantum spectrum shows tell-tale pre- and post-resonant signatures which include attraction of quantum
levels (rather than the usual Fermi repulsion) and other features not normally associated with Fermi
resonances. Evidence is presented which suggests that certain types of periodic motion in anharmonic
molecules act as "traps", and are resistant to energy exchange with other types of motion. Numerical
evidence linking the classical and quantum behavior, together with a new semiclassical theory presented
here provides a very explicit connection between quantum and classical anharmonic motion.

I. INTRODUCTION initial conditions. For example, in a harmonic potential,

Much research has been focused recently on the ques-
tion of intramolecular energy transfer. I The importance
of this process to many areas of chemical physics is
obvious. In this paper, we concentrate on a specific
aspect of intramolecular energy redistribution which
seems to have been passed by. Although impressive re-
cent advances in the theory of the onset of stochastic
motion in classical anharmonic systems have spurred
studies of the parallel quantum mechanical problem,t,2
we emphasize that the present study does not concern
the stochastic transition. Instead, we study a much
simpler dynamical property, which is well understood
classically, but which nonetheless has important impli-
cations for energy redistribution. The parallel quantum
problem seems to have been only obliquely examined.
Since it is so much simpler than the question of stochastic
motion, we are able to make a very specific connection
between the classical and quantum mechaniCS, linked in
this paper by numerical evidence and a firm semiclas-
sical theory.
The dynamical property which is studied here involves
the decay (or lack of it) of one mode of molecular motion
into another. This sounds very much like the question
of stochastic motion, but it is not. We are concerned
here with individual mode-mode resonances in restricted
regions of the phase space of the molecule. A beautiful
picture of the onset of stochastic motion involves the
overlap of two or more such resonant regions in phase
space. a Isolated resonances may exist which strongly
couple the modes, yet because of the isolation, the mo-
t ion remains quasiperiodic.
The modes to which we refer are periodic motions of
the molecule, which can always be found for certain
aWork supported by NSF Grant No. CHE77-13305.
b)Alfred B. Sloan Foundation Fellow: Camille and Henry
Dreyfus teacher scholar.
all pure normal modes (energy totally in one mode) give
rise to periodic orbits. When small anharmonicity is
introduced, these closed orbits will not disappear, but
will be found near by in phase space. In addition, new
periodic orbits may appear which, however, have larg-
er periods then the "fundamental" set of perturbed
closed orbits. We shall for now focus on a special type
of periodic orbit which is easiest to visualize and very
relevant experimentally as well. This is totally sym-
metric motion in a molecule which has exactly one such
mode, including anharmonicities. Examples are CO2 ,
BFa, SFs , CH 4 , etc. Water will not do, because an-
harmonic terms come in to mix the symmetric stretch
and the symmetric bend, both of Al symmetry. The
approach we describe is by no means limited to this
case, and a future publication will deal with more gener-
al types of motion. The experimental relevance comes
from the fact that Franck-Condon transition often in-
volve displacements only in the totally symmetric stretch
coordinate. To find these periodic orbits numerically
merely involves initiating the system with positions and
momenta belonging to the totally symmetric representa-
tion of the group of the molecule.
If the molecule could be represented by a point in
phase space, with a totally symmetric initial condition
as just described, then symmetry requires that it for-
ever exhibit pure symmetric stretch motion, even in
the presence of anharmonicities. Quantum mechanically,
however, in a Franck-Condon transition involving a dis-
placement in the totally symmetric coordinate, one has
a wavepacket with a certain extent in position and mo-
mentum surrounding the purely symmetric stretch phase
space point. Therefore, it is reasonable that we should
consider the history of trajectories which begin in some
sense nearby the totally symmetric configuration. A
confusion often arises in the quantum mechanical case:
It seems paradoxial that energy could flow into unsym-
metric modes, subsequent to the Franck-Condon transi-
tion, even though the initial Franck-Condon wavepacket
belonged only to the totally symmetric representation.

4720 J. Chern. Phys. 73(10), 15 Nov. 1980 0021-9606/80/224720-16$01 .00 © 1980 American Institute of Physics
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 Heller, Stechel, and Davis: Molecular spectra
However, the system is allowed to couple into all over-
tones and combinations involving unsymmetric modes
whose direct product nonetheless contains a component
in the totally symmetric representation, so there is no
paradox. A complementary point of view, and one which
is important for the' interpretation of the analogous clas-
sical mechanics, is that a wave function may belong to
the totally symmetric representation of the molecule,
and yet possess amplitude in regions of configuration
space which do not have this symmetry. (This simple
fact accounts, for example, for vibronic allowedness
in so called electronically forbidden transitions. )
If a periodic orbit is stable, then trajectories begin-
ning in the vicinity of the periodic orbit are never able
to wander very far. The "vicinity" surrounding a stable
or elliptic fixed point can be quite large or arbitrarily
small in classical mechanics. It seems fairly reason-
able that for the stable nature of a periodic orbit to sig-
nificantly affect the corresponding quantum mechanical
Situation, the stable vicinity must compare favorably
with a elementary quantum volume in phase space, i.e.,
Planck's constant h (or some appropriate power of it
depending upon the dimension of the phase space).
Classical details on a finer scale than this should some-
how be washed out or averaged over.
If a periodic orbit is unstable, then initially close tra-
jectories may wander quite far from each other, leading
for example to energy exchange. If the symmetric
stretch frequency (which is in general a function of the
total energy in the symmetric stretch) satisfies low
order "resonance" conditions with one or more other
modes, then relatively small anharmonic coupling be-
tween the modes can cause instability leading to flow
from the symmetric stretch into the resonant mode.
The resonance conditions are simply ws "" w. (1: 1 reso-
nance), w.",,2w. (1: 2 resonance), 2w s ""w. (2: 1 reso-
nance), etc. 4 If the resonances are not very close, then
stronger anharmonic coupling is required to cause the
motion to become unstable. Since in general the effec-
tive frequencies change with total energy, and the effec-
tive anharmonicity steadily increases with total energy
there can be a complex interplay of these two effects,
and it is possible for the symmetric stretch periodic
motion, or for that matter, any periodic motion to con-
tinuously evolve from stable to unstable and back again,
and so on as total energy in the periodic mode is in-
creased. For the systems we investigate here, there is
a simple evolution from stable to unstable, and whether
more complex behavior is important for realistic poten-
tial surfaces is an interesting matter for future research.
Now consider the quantum mechanical situation. As
pOinted out by Herzberg,5 the factors causing coupling
and instability of two degrees of vibrational motion in
the molecule are the same both classically and quantum
mechanically. Using perturbation theory for example
(see Sec. II. E) we see that the first feature mentioned
above, namely, near resonance of fundamental frequen-
cies, would lead to small energy denominators in the ex-
preSSion for the perturbed wavefunction. Similarly,
the second feature, namely the strength of the interac-
J. Chern. Phys., Vol. 73, No. 10, 15 November 1980
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4721
tion, would lead to large numerators. The prototypical
behavior in the quantum mechanical situation is for a
pair of nearly degenerate quantum levels arising from
nearly resonant fundamental frequencies to interact
strongly through the introduction of the anharmonic
terms; this interaction is often noted in the spectrum
through the mutual repulsion of the energy eigenlevels
from their zero order positions, and from "intensity
borrowing" which arises from the strong mixing of the
zero order states. The repulsion and mixing are the
hallmarks of a Fermi resonance. In general, the situa-
tion is more complicated than this because there are
many zero order levels which are approximately degen-
erate. For example, in the 1: 1 resonance, between two
modes "s" and "u," the levels (n .. 0), (n s -1,1),
(n s -2,2), etc., may all be approximately degenerate.
The relationship between the classical stability of the
modes, and the fate of these zero order levels (i. e.,
their spacing and their appearance in the spectrum)
under the influence of the anharmonic terms, is the
main subject of this paper.
The above discussion is meant to provide a rough in-
tuitive framework for the more general picture of Fermi
resonances and their relationship to classical motion
which is emerging from the more detailed considerations
presented in the sections that follow. One of our main
points is that it may just happen that the classical insta-
bility, which our experience and explicit calculations
have shown to very profoundly effect the quantum spec-
trum, sets in above an energy corresponding to several
symmetric stretch quanta. It turns out that this leads
to a rich signature in the spectrum entailing "prereso-
nant attractions, " "post-resonant broadening, " and other
features which seem not to have been associated with
Fermi resonances in the past. Even in the case that the
classical instability occurs well before the first reso-
nant levels in the absorption spectrum, (and this is the
case that has traditionally been associated with Fermi
resonance in the past) we can still extract some infor-
mation about the degree of classical instability (in the
vicinity of the symmetric stretch) from the width of the
quantum absorption symmetric stretch bands, and vice
versa.
In Sec. II we present results of classical and quantum
calculations which provide strong empirical evidence for
a close link between the stability of classical motion and
corresponding quantum effects. In Sec. III, we provide
a semiclassical theory which solidifies this relationship.
In Sec. IV, we present a discussion of the Significance
of these results, including some speculations on the pos-
sible important role played by certain types of periodic
stretch motion in trapping energy in molecules.
II. CLASSICAL AND QUANTUM EVIDENCE OF
INSTABILITY
Before presenting a semiclassical theory (in Sec. III)
linking quantum spectral features to classical dynamics,
we expose here some evidence of the connection, mostly
in the form of pictures, obtained from converged quan-
tum, classical and semiclassical numerical calculations.
 4722 Heller, Stechel, and Davis: Molecular spectra

10

..... :, ..

ENERGY
FIG. 1. "Master diagram." The spectrum at the bottom arises out of the Hamiltonian! +! p; p;+
V(s ,u) [see Eq. (2.1) for V(s,u)]
and the displaced wavepacket Eq. (2.3). The arrows point to the lines in the symmetric stretch Franck-Condon spectrum corre-
sponding to the wavefunctions. Since the strongest lines were selected, the wave functions (plotted as contour diagrams for liJlI2 at
the top) have maximum symmetric stretch character in their respective energy domains. Also shown are the time averages of
trajectories and u, p. surfaces of section (second and third rows), both at the same energy as the corresponding wave function.
See text for further details.

A. The master diagram
Figure 1 can be regarded as a "master diagram" for
the major points we wish to make. In it will be found
(i) the Franck-Condon spectrum for a displaced wave
packet in the anharmonic potential
(2.1)
with Ws =1. 0, w. =1. 1, and'\ = - 0.11 (»is =m. =1. 0); (ii)
plots of IlJIn(s, u) 12 for selected eigenstates n which ap-
pear with significant intensity in the spectrum; (iii) time
averages of classical trajectories whose total energy
equals that of the wavefunction beneath which they ap-
pear; and (iv) surfaces of section for these tra-
jectories (and others "nearby" in their initial conditions)
in the u,P. plane. As the energy increases in Fig. 1,
changes take place which are directly reflected in all
four features just mentioned. We now give a discussion
of these effects.
First let us focus on the spectrum in Fig. 1. The
wavepacket, which may be thought of as coming from
another potential surface with a displaced equilibrium
position in the symmetric coordinate s, generates a
spectrum via the Franck-Condon factors
in = I<n I ¢) 12 , where In) is the nth eigenstate and I ¢) the

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 Heller, Stechel, and Davis: Molecular spectra 4723

TABLE 1. Pre resonant attraction of levels. Also, they get progressively closer together as energy
increases and they begin to grow somewhat in intensity.
Ea (n.,n u) Further, the combinations cannot be to disappear
2.0450 (1,0) 0.0912 0.0921 0.094 from this spectrum by taking a symmetrically displaced
2.1362 (0,1) wave packet with different exponential parameters; in
3.0415 (2,0) 0.0854 0.174 0.0869 0.087 fact changing the frequencies in the ground and excited
3.1269 (1,ll state [this would mean Wu appearing in cp would be dif-
3.2157 (0,2) ferent from ,that in the potential Eq. (2.1)1 increases the
4.0373 (3,0) 0.0785 0.164 0.0817 0.078
intensity of the combination lines. If >.. were set to zero,
4.1158 (2,1) and everything else were the same in our calculations,
4.2008 (1,2) only a simple symmetric stretch progression (one line
for each value of n.) would be seen. Thus we are forced
5.0323 (4,0) 0.0704 0.150 0.0765 0.068
5.1026 (3,1) to associate the residual combination intensity with an-
5.1827 (2,2) harmonic coupling between the modes. The second
notable feature is the dramatic growth in the number of
6.0260 (5,0) 0.0608 0.135 0.0713 0.055
(4,1)
combination peaks per n. band and a sharing of intensity
6.0868
6.1611 (3,2) as energy (thus n.) increases past E""S.O. The zero
order labeling (n., 0), etc., begins to lose Significance
7.0182 (6,0) 0.0491 0.118 0.0661 0.036
as this mixing occurs and the n. bands begin to acquire
7.0673 (5, II
7.1357 (4,2) an envelope with a width that increases as energy in-
creases. The zero order state (n.,O) has been broad-
8.0082 (7,0) 0.0348 0.0979 0.0608
ened and some sort of lifetime is associated with the
8.0430
8.1061
(6,1)
(5,2)
width of the set of lines belonging to a given n..
Clearly,
this lifetime is connected with the decay of the zero
aH = +! w;
+! S2 +Au 2S, where Wu = 1.1, w.= 1. 0, order state (n.,0), but more Significantly we shall be
>"=-0.11, able (below) to relate it with the classical rate of exit
btl.jE= 1E(n.,0)-E(n.-1,lll, zerothorder=O.1. from the symmetric stretch region. The lifetime has an
ctl.2E = 1E(n., 0) -E(n. - 2, 2) 1 , zeroth order = O. 2. indirect link with the lifetime of energy in the s mode,
dt;E perturbative for b.
et;E semiclassical, determined from trajectory and stability Next we consider the wave functions 6 associated with
parameter at the quantum energy minus the zero point energy the peaks selected by the arrows in Fig. 1. Since the
(1. 05 in this case). Instability occurs at E clao. = 6. 8, or selected peaks have large Franck-Condon intensity and
Equant = 7.8. since cp is displaced along the symmetric stretch, we
would expect the wave functions to have significant prob-
ability along the symmetric stretch, and this is indeed
displaced wavepacket. The spectral lines have been the case. The outline surrounding each wave function
artificially broadened with a Gaussian line shape, lead- is the eqUipotential contour for energy equal to that of
ing to the eigenfunction; thus, it forms the boundary where
(aside from slight tunneling) the wave function can be
found. We see that indeed the wave functions have much
symmetric stretch character, but they become increas-
where T=57, and Wn is the nth eigenvalue. The wave ingly distorted as energy increases, until at the highest
packet cp is given by energy they have enough amplitude outside the symmet-
ric stretch region to drastically reduce the Franck-
cp(s, u) =(w. Wul1T2)1/4 exp[- (w./2)(s _4.0)2 - (w u /2)u 2 J. Condon overlap, and indeed no wave function can be
(2.3) found which looks like a localized symmetric stretch in
this energy region. (On the other hand, none is found
This is the ground eigenfunction of a surface displaced
which covers the allowed coordinate space more or less
4.0 units in s, with the same fundamental frequencies
evenly, either. It can easily be shown that in two di-
w., wu' There are two notable features of the spectrum,
mensions' a "stochastic" eigenstate would possess an
aside from the fundamental symmetric stretch pro-
even distribution of probability over the allowed x-y
gression and the overall breadth of the absorption band
region, after which it would fall off rapidly. The even
(which arise from periodic motion in the s coordinate
distribution would be locally mOdified by nodal struc-
and the steepness of the potential in the Franck-Condon
ture.) At high energies (E > S) it is evident that many
region, respectively): The first is the presence of side
states now share the symmetric stretch character which
peaks at low energy which grow in intensity as energy is
belonged to the (n.,O) zero order state.
increased. These represent combination overtones of
the type (n s -2,2), (n.-4,4), etc., built upon the main Associated with each wave function is the time average
(n., 0) progression seen at lower energy. [The (n. -1,1\ of a particular (single) trajectory, shown below the cor-
etc., lines are missing because they are odd functions responding wave function in each case in Fig. 1. Just
of u while cp is an even function, i. e., they vanish by as the wave functions split up into various classes in a
symmetry.J According to the fundamental frequencies, given energy range, so too do the trajectories, and the
these combinations should be split by 0.2 units. In- trajectories shown are selected to give good corre-
stead, they are all split by less than this (see Table I). spondence with their associated wave functions. Still,

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 4724 Heller, Stechel, and Davis: Molecular spectra
the detailed agreement is almost incredible, and it is
not hard to find trajectories which correspond equally
wei 1.7< a) The classical motion remains mostly integrable
at all the energies shown in Fig. 1, except perhaps the
highest, so one expects the trajectory-wave function cor-
respondence to be close, given the success of semi-
classically quantizing such systems. 7-10 For the pres-
ent, this close correspondence between classical mo-
tion and quantum wave functions provides a strong sug-
gestion that the classical motion might tell us something
about informative details of the spectrum, both qualita-
tively (what does the mixing of intensity seen at higher
energy have to do with stability of classical motion?)
and quantitatively (can trajectories run on the potential
surface predict spacings, intensities, and bandwidths?)
(answers provided below!).
Lastly, Fig. 1 shows u,P u Poincare surfaces of sec-
tion for three trajectories at each of the four energies.
These prove to be very informative and crucial to the
semiclassical analysis of Sec. III. This surface of sec-
tion4 amounts to plotting the value of u and Pu every time
°
a running trajectory penetrates the s = line with Ps > 0.
°
Since the trajectory with u = Pu = is necessarily stuck
on the symmetric stretch line forever, this point on the
surface of section represents a fixed point through
which this special trajectory must pass each period in
the s-motion. If either u or Pu are non vanishing, then
successive passes through s =0 give rise to character-
istic patterns in the vicinity of the fixed point. For
example, at low energy the fixed point is surrounded
with roughly elliptic curves each formed by the repeated
passes of a single trajectory. If the trajectory passes
very close to the fixed point in the u,Pu plane, it re-
mains forever close in this low energy regime. This is
tantamount to saying that a small amount of energy in the
u mode remains forever small, and this is what happens
at lower energy. However, at E =6.8, the central fixed
point becomes hyperbolic, and now a small amount of
energy in the u mode will grow in time at the expense of
energy in the s mode; later it will eventually return to
the s mode, etc. Thus above E = 6.8, the symmetric
stretch motion has become unstable. Classically, a
resonance has set in between the sand u modes above
E =6. 8 and these two modes are freely exchanging ener-
gy. All four features shown in Fig. 1 herald the onset
of the s-u resonant instability by switching gradually
from preresonant behavior to post-resonant behavior
in the vicinity of E"" 7.8, which is the classical reso-
nance energy plus the zero point energy of 1. 05.
Although technically there is an abrupt change of the
stability of the fixed point, from elliptic to hyperbolic,
near E =6.8, the volume of phase space which is affected
by the hyperbola is at first quite small. That is to say,
a technically unstable trajectory in the close vicinity of
the fixed point follows a hyperbolic path in the surface
of section which travels only a short distance from the
symmetric stretch fixed point before returning, and tra-
jectories further from the fixed point behave still as if
they surround an elliptic point. At higher energy the
volume of phase space occupied by the hyperbola is much
larger. Thus even in the classical mechanics the turn-
over to instability is smooth if viewed in this way. On
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the other hand, the quantum wave function r/J, which oc-
cupies a finite volume in phase space, is seriously af-
fected by the instability (as seen in the spectrum) only
after the hyperbolic region has grown to significant size.
(The size of the wave packet is shown in one of the eigen-
function plots in Fig. 1). Thus, as seen in Fig. 1, the
real growth in the combination line intensities occurs
only after the symmetric stretch has become unstable.
B. Relation to Fermi resonance
So far we have seen that the spectrum, wave functions,
classical trajectory time averages, and classical sur-
faces of section, all act in parallel and definitely show
the effects of a transition to unstable symmetric stretch
motion, with concomitant energy exchange between sand
If. What has all this to do with the notion of Fermi
resonance? As mentioned in the introduction, the pro-
totype Fermi resonance 5 involves a pair of levels which
mix strongly and repel one another. When this behavior
is "chronic" in the sense that there are many states
[(n., 0), (n s -1), 11, and possibly (n s - 2,2), (n s - 3,3),
etc; = 1, 2, ... , where w s "" wu , then, as mentioned
before, the resonance is expected to occur both classi-
cally and quantally. For the system in Fig. 1, the reso-
nance has waited until E = 7.8 to set in. Above this ener-
gy, there is a classical resonance, and the new spectral
features and qualitati ve changes in the wave function
strongly suggest that the designation" Fermi resonance"
be aSSigned to the E >8 region for this system, but not
for E < 8. Clearly, this means we cannot always rely
upon the classic intensity sharing and splitting of a pair
of levels as a means of detecting a Fermi resonance. In
this particular case, the system was not resonant at
E "" 3.0, when only a pair of levels, namely (2,0) and
(0,2) were available to interact with each other. [The
(1,0), (0,1) levels give rise to a pair of levels, one of
which is miSSing from the spectrum by symmetry, see
Table I for the energies, however. 1 Indeed, the (2, 0)
and (0,2) levels attract each other relative to zero order
positions, and share intensity weakly. This is an exam-
ple of what we term preresonant behavior. Later we
shall see that pre resonant effects can also include re-
pulsion of levels (but still very little mixing). This is
another sign that to look only for the "classic" signs of
Fermi resonance is somewhat misleading.
Under what circumstance, then, do we get the "clas-
sic" Fermi resonance?l1 We maintain that the
case of strong mixing and repulsion of the first pair of
levels that can possibly interact (as in CO 2 , for exam-
ple 11 ) simply corresponds to the event that the classical
motion is unstable well below the energy of the inter-
acting pair! Figure 2 shows a Franck-Condon spectrum
for a case that was chosen to correspond to the CO 2
symmetric stretch-to- bend interaction. As mentioned
in Ref. 11, symmetric stretch classical trajectories
run on the surface were unstable above about 20 cm- 1 of
energy, well below the first energy levels of the system.
As expected, the first pair of levels are repelled and the
spectrum (Fig. 2) shows also the mixing and broadening
of all the higher overtone bands.
Note that for the case of 1 : 1 resonance between two
 Heller, Stechel, and Davis: Molecular spectra 4725

modes coupled by a >..su 2 cubic anharmonicity, the matrix

elements between the interacting levels (n.,O) (n. - 2,2),
etc., vanish. This illustrates that it is certainly pos-
sible to have Fermi resonance effects even though there
is no first order coupling, although resonance is cer-
tainly "easier" if there is such a coupling. This too
has a direct classical counterpart, as we see below (Sec.
lID and lIE).

C. Qualitative semiclassical picture: Spectra from

classical trajectories
Considerable qualitative insight into the relationship
of the quantum and classical mechanics of stable and un-
stable periodic motion can be gained from a time de-
pendent picture of molecular electronic spectra. 12 Fig-
ure 3 shows a typical anharmonic two-dimensional po-
tential surface, which might correspond to symmetric
and unsymmetric stretch motion of a symmetric tri-
atomic molecule. Supposing that an electronic transition
has occurred, the Franck-Condon wave packet from the
ground electronic state may find itself displaced from
equilibrium in the excited electrOnic state, as shown in
Fig. 3. The spectrum of the system is given by12
(2.4)
24.0
12.0
FIG. 3. Potential surface of Eq. (2. 1) with displaced wave
packet of (2.3) shown. This situation generated the spec-
trum of Fig. 1 via Eq. (2. 2).
where Eo is the energy of the ground state IX) of the
lower potential surface; w is the frequency of the inci-
dent radiation; 1<fl)=IJ.IX), where IJ. is the transition mo-
ment between the two surfaces (a constant in the Condon
approximation); and I <fl(t) is the solution of the time de-
pendent Schrodinger equation on the new potential sur-
face with 1<fl(0)= l<fl). Equation (2.4) says that every
feature in the absorption spectrum can be obtained from
knowledge of the evolution of the wavepacket I <fl(t) on
the new potential surface. More specifically, only the
overlap of this evolving wavepacket with itself at time
t =0 is required. The time -frequency uncertainty prin-
ciple guarantees that short time dynamics of I <fl(t» will
determine the broadest features of the absorption spec-
trum, and long time dynamics of <fl(t) influences detailed
features of Given the situation shown in Fig. 3,
the wavepacket I <fl(t) will abruptly leave the Franck-
Condon region where <fl resides, and the resulting decay
of the overlap will determine the width of the absorption
band. Of course, the steeper the potential surface in
the direction of the symmetric stretch, the more rapid
the decay of the overlap, and the broader the absorption
band This decay is visible as the first peak near t =0
o

in Fig. 4. The second time of interest for the situation

shown in Fig. 3 is the period of the symmetric stretch,
since this is the time at which the wandering wave packet
I <fl(t) returns to the initial Franck-Condon vicinity and
again has significant overlap with <fl. However, upon

FIG. 2. Franck-Condon spectrum for CO2 Fermi resonance.

v(s ,u) =! s2 +! (0. 49796)2u 2 - 2
O. 037su , which mimicks CO2 (see '-
'-
'-
Ref. Ill. The displaced wave packet is the ground state of the
harmonic part of V(s,u) displaced to s =2. 0, where s is the
symmetric stretch and u represents the bend coordinate. The
entire spectrum is post-resonant (or Fermi resonant). In this 0.2
system of units, the energies are multiplied by 1353 to obtain
vibrational eigenvalues in cm- t • The FWHM bandwidth of the
0.0 .0
set of lines belonging to the zero order state (2,0) near E = 2.75
is 0.095 or 130 cm-I, or a lifetime of about ten symmetric TIME
stretch vibrational periods (0.3 psecl. The stability parameter FIG. 4. Magnitude of the correlation function I (¢ I ¢(t» I for
r. (see Sec. uI> is 0.086 or 116 cm-t • the system of Figs. 1 and 3.

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 4726 Heller, Stechel, and Davis: Molecular spectra

this return and subsequent returns the evolving I q;(t) 3

will in general have a reduced overlap with I q;(0).
Nonetheless, this periodic function in time (see Fig. 4)
l: 2
leads in turn to the symmetric stretch vibrational pro-
gression which is expected in frequency. Notice that 1
our discussion of these first two characteristic times in
the overlap has been couched in classical terms: the O. 4. 12.
rate of the initial falling away of I q;(t», which is deter- E 8.
A
mined by the steepness of the potential surface in the 20
direction of steepest descent, and the periodicity of the
motion in the symmetric stretch. l:
10
The third characteristic time affects the higher reso-
lution details of the individual vibrational overtone fea- 04 .75
tures seen in the spectrum. These features, which are 5.75 B
our main concern in this paper, may also be derived
classically. In fact, the classical determinant of this
higher resolution structure is indeed the stability of
symmetric stretch motion. Accepting for the moment l:

;1
that the classical trajectories in the vicinity of the
Franck-Condon wave packet evolve in much the same
way as the wave packet itself, at least for moderately
short times, it is apparent that if the trajectories suffer 15.5 16.0 16.5
unstable falling away from the symmetric stretch region E C
into remote regions of coordinate space, then the first
few return visits of I q;(t) may result in progressively FIG. 5. Potential is (1.818181)2s2+0.1su2, the
weaker overlap with q;. The decreasing peak values of displaced Franck-Condon wave packet is the ground state of the
I (q; I q;(t) I (for the first few vibrational periods) can be harmonic part of V(s, u) displaced to s = 1. 54 in (a) and (b), and
to s = - 2.52 in (c). In (a), the "low resolution" spectrum is .
seen in Fig. 4. If the envelope of this decrease were to
seen for both the exact [Eq. (2.2) with T = 7] and semiclassical
be continued (dashed line in Fig. 4), there would result [Eq. (2.4)]' with q,(t) determined by the trajectory cluster
a true, unresolvable broadening of the symmetric method of Ref. 13 with the argument of Eq. (2.4) multiplied by
stretch peaks (this is in fact what occurs for certain un- exp(- t2 /2T 2 ), T = 7. The two spectra are virtually indistinguish-
bound potential energy surfaces 12 ). In fact, because the able. In (b), one of the overtone lines is examined at higher
potential surface is bound, new recurrences come in at resolution, showing a difference in the semiclassical (dot-dash)
longer times. These ultimately determine the structure and exact combination line. In (c), the displacement of q, puts
which is present under the otherwise broadened peaks. it in the unstable region, and the semiclassical method gives
the correct envelope. The areas under the two curves are
identical. T = 57 in both.
If the symmetric stretch motion is stable, then there
will be structure in the time domain coming in after a
time equal to the reciprocal of the frequency splitting of
the combination-overtone pairs seen below resonance. because of the logical sequence
Even though the wave packet which was used to generate
I (q; I q;(t) I in Fig. 4 has an average energy above the classical trajectories
threshold resonance energy, the spectrum still encom- I
passes some of the stable region and thus one does in- q;(t)
deed see this recurrence building up after t "'" 40. The I
semiclassical method described below for generating I
(q; q;(t)
spectra from trajectories solidifies the trajectory -spec- I
t rum connection. Z;(w)

It ;i.s a very successful semiclassical method for generat-

Some time ago, a method was developed in this lab-
oratory for determining the evolution of the state q;(t)
from classical trajectories. 13,14 Briefly, a cluster of
five classical trajectories is run (2N + 1 in the general
case, where N is the number of spatial dimensions) with
initial conditions all near the average pOSition and mo-
mentum of the wave packet; then the overlap and Fourier
transform in Eq. (2.4) are performed, leading to a spec-
trum. The method is approximate, and relies upon a
local linearization of the classical dynamics. To the
extent that it works, it provides a very explicit connec-
tion between the classical mechanics and the spectrum,
ing spectra, because as Fig. 5 shows, not only are line
positions available, but intensities as well. At a certain
level of resolution, the exact quantum spectrum and the
semiclassical one are indistinguishable [Fig. 5(a)]. At
higher resolUtion, but below threshold for instability the
combination-overtone peaks are seen [Fig. 5(b)1. The
side peaks occur at an energy determined by periodici-
ties in the trajectories which give rise to our semi-
classical q;(t). Above instability, the linearized tra-
jectories "think" the motion is permanently unstable,
giving rise to broadened peaks in frequency. As Fig.
5(c) shows this broadened peak contains information

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 Heller, Stechel, and Davis: Molecular spectra 4727

gg :.0
a 0.8
0.6
0.4
0.2
0.5

FIG. 6. Stability plot for the Mathieu equation. Shaded regions are unstable, ,f(i=2wjw s ' where So is the displace-
ment of the s oscillator. Dashed lines show the stability parameter 11= I v I /rr in the stable regions, s in the unstable regions.
From M. Abramowitz and A. Stegun, Handbook of Mathematral Functions (Dover, New York, 1965>'

about the envelope of the actual high resolution lines values of q. Note that q is proportional to the anhar-
seen in the exact quantum calculation. The strong link monic coupling A times the square root of the energy.
between the classical mechanics and the spectrum pro- The higher resonances become increasingly narrow, at
vided by the wavepackets is part of the motivation for least for small values of q. (ii) The onset of instability
the semiclassical theory presented in Sec. TIL is more sudden, severe, and occurs for smaller values
of q ex..fE if a is on the "high Side" of exac t resonance,
D. Mathieu equation model for stability i. e., if Wu > Ws in the 1 : 1 case, etc. This is a strong
effect and it gets stronger as the resonances get nar-
In 1961, Thiele and Wilson 15 investigated the role of
rower. In Sec. III, we shall make use of the dashed lines
anharmonicity as a determining factor for a dissociating
appearing in Fig. 6; they will help predict spacings and
symmetric triatomic molecule. They recognized the
bandwidths of the combination-overtone ensembles.
stability of the symmetric stretch mode as a strong in-
For now, we restrict attention to the qualitative changes
fluence affecting energy flow in the molecule. As they
in the spectrum as resonance is approached and sur-
pointed out, much can be learned about the dynamics
from a consideration of the stability of Mathieu's equa- passed. While Fig. 1 is fairly unequivocal about this
tion. 16 Starting from Eq. (2.1), it is easy to see how relation, perhaps Fig. 7 will add further insight. In
the Mathieu equation arises. If nearly all the energy is Fig. 7 the stability diagram is shown "sideways" and
E ex q2 is plotted instead of q. Three different spectra
initially in the s mode, then it is reasonable to assume
that s behaves as
(2.5)
(assuming without loss of generality that Ps =0 at t =0),
at least for relatively short time. Equation (2.5) is the
exact solution for the pure s-mode periodic trajectory.
Assuming this zero-order motion in the s mode, then
the u mode may be considered separately, with a time
dependent Hamiltonian given by
(2.6)
If we set T=%Wst, ,fa =2w ulw., and q=4Asolw!, we have
the classical equation of motion
2
yd u
+ (a -2qcos2T)U =0 , (2.7)

which is Mathieu's equation. The solution u(t) to this 1.5 ----------- -

equation tells us about the early time evolution of energy
in the u mode. The Mathieu equation is well studied,
and its stability as a function of a and q is shown in
Fig. 6. The shaded region corresponds to instability,
FIG. 7. 1: 1 resonance region of Fig. 6 (Yli =2), plotted as E
which is more severe the deeper the penetration into the
vs ra" 2wjw 8' Three spectra with baselines appearing at the
unstable region. Two conclusions are immediately ap- value of ra appropriate for each of the three potentials generat-
parent from Fig. 6: (i) The 1: 2 resonance is the broad- ing the spectra are shown. Note the qualitative change in the
est in the sense of being easiest to reach with modest quantum spectrum as the classical resonance region is entered.

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 4728 Heller, Stechel, and Davis: Molecular spectra
are shown qualitatively, where the abscissa baseline
has been drawn at the appropriate value of 2wuiw., and
the spectrum is also plotted as a function of E. Note
how the spectrum changes as energy increases into the
resonance region, and how the resonance energy is very
dependent upon the value of 2w u /w.. Note the decrease
in spacing of the lines before resonance is reached for
the two cases shown where Wu > w.. Compare the far
greater stable region for the Wu < Ws case.
So far, our discussion has been in terms of the poten-
tials of the form (2.1). One may well ask, what is the
effect of higher order (and other cubic order) anhar-
monicities? In general, the stability plot such as Fig.
6 will change, and will correspond to stability of Hill's
equation,16 of which the Mathieu equation is a special
case. The stability map can be determined by running
trajectories for a short time (see Sec. Ill). Once the
stability has been determined, the same strong correla-
tions will follow between the classical and quantum be-
havior. This will become much more evident below, as
the semiclassical foundations of the correspondence are
explained.
E. Perturbation theory
Second order nondegenerate perturbation theory can be
applied to the eigenvalues (the first order shift vanishes).
This predicts the correct trend toward attraction of
levels in the case shown in Table I (other cases can show
repulsion of levels in the preresonant regime, both in
the exact and perturbative calculations), but the esti-
mated magnitude of the pre resonant attraction is too
small and contains no hint of the onset of the resonance.
Note that even the first pair, namely, (1,0) and (0,1),
are "attracted" to a separation of 0.0912 from an un-
coupled value of 0.1 in the 1: 1 resonance case of Table
I. However, these levels are of different symmetry
(even and odd about u = 0) and do not interact in any order.
Still, they fit in to the total pattern of level splittings,
and even perturbation theory predicts an attraction. One
should not conclude that the levels must be of different
symmetry for the attraction to occur. Examine the
(2,0) and (0,2) levels, which do interact and are at-
tracted to a splitting of 0.174 (0.2 in absence of coupling)
and the (2,0) and (1,1) levels, which do not interact but
1I0netheless are split by almost exactly half that of the
(2,0), (2,2) pair. One would expect this since the latter
differ by two quanta and the former, by only one.
The semiclassical theory of Sec. III makes no dis-
tinction between pairs of levels which do or do not inter-
act; they must all fall into a regular pattern and, indeed,
Table I shows they do.
In the previous section, we noted that the 1: 2 classi-
cal resonance was the "broadest" in the sense that the
unstable region is easiest to reach as a function of ener-
gy or anharmonic parameter (A). Quantum mechanically
this shows up in the existence of a first order coupling
matrix element between, e.g., (2,0) and (1,2). Above,
in the 1: 1 case, there are no first order couplings be-
tween, e.g., (2,0) and (1,1).
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III. SEMICLASSICAL THEORY OF ANHARMONIC
SYMMETRIC VIBRATION SPECTRA
We now examine a simple semiclassical theory which
is capable of describing and predicting all the major
features seen in the preresonant and post-resonant
Franck-Condon spectra shown in Fig. 1.
A. Quantization of the effective Hamiltonian
Some time ago, Gutzwiller l7a made a study of classical
periodic orbits and their relation to the quantum density
of states. He made clear the importance of considering
the stability parameter of the orbit (see beloW), and
pointed to certain difficulties of interpretation if the
orbit is unstable. Gutzwiller's work and the work of
Miller 17b assumed one quantum condition per periodic
orbit. Then Marcus, 7c Noid and Marcus, 7b and Milier l8
noted that, in general, N -1 additional quantum condi-
tions were required. However, this too was shown by
these workers to be ambiguous at best and wrong in sev-
eral respects. Miller's work, 18 which assumed that the
orbit was stable, concluded with the observation that the
positions of the eigenvalues were incorrectly predicted
for certain anharmonic potentials, which would include
Eq. (2.1), for example. Berry and Tabor l9 raise a re-
lated objection in that the stability parameter analysis of
periodic orbitsl7,lB breaks down if the closed orbits are
not isolated; this is one reason for inaccuracy of the
semiclassical eigenvalues. Also Noid and Marcus 7b
showed that many completely spurious eigenvalues are
found if periodic orbits are used to quantize the system.
Against this historical backdrop, we focus on our
specific requirements in attempting to describe a spec-
trum such as that seen in Fig. 1 in terms of classical
theory. Below the classical resonance (or instability),
we need to know the spacing of the combination-overtone
lines, and for this the periodic orbit theory should be
useful, 7a,17-19 notwithstanding the problem of incorrectly
predicted energies mentioned above. We need also to
be able to predict the intensities of the combinations,
relative to the pure overtones, below resonance. Final-
ly above resonance, we abandon the description of the
individual lines, and instead we try to describe the band-
width for the set of lines corresponding to what would
have been the single line (n., 0) in the absence of coupling.
The periodic orbit methods, based as they are on the
density of states, say nothing about the relative intensi-
ties of the lines in a particular Franck-Condon spectrum.
There is simply no information in the density of states
about the initial state (what we call ¢) which generates
the intensities via Franck-Condon factors or, equiva-
lently, via Eq. (2.4). For the same reason, no explicit
interpretation is given to the stability parameter (see
below) in the above resonance case, where it is no longer
simply related to the level spacings. More accurate
semiclassical quantization methods based on a full ac-
tion-angle variable treatment (instead of stability par-
ameters) have been successfully applied to the Fermi
resonant case. 7a However, intensities were again not
available, so accuracy of eigenvalues was stressed,
rather than the "spectral signature" of a Fermi reso-
nance which we emphasize here.
 Heller, Stechel, and Davis: Molecular spectra
Because of such deficiencies of existing periodic orbit
theory, we adopt a different approach which provides in-
formation about intensities and bandwidths. Simulta-
neously, we shall learn that the eigenvalue positions
which are most prominent in the spectrum are most ac-
curately predicted.
Our approach is motivated by consideration of the time
dependent overlap in Eq. (2.4) and the qualitative semi-
classical picture of Sec. II. C, especially as applied to a
symmetrical stretch. 12 The idea is as follows: A wave
packet ¢, which is relatively localized, can be accu-
rately propagated by assuming linearized dynamiCS in
the vicinity of the center of the wave packet. This as-
sumption, which implies that positions and momenta
are linear functions of initial positions and momenta,
is equivalent to the trajectory cluster method of propa-
gating wave packets semiclassically, discussed in Ref.
13. For the present case of a totally symmetric
stretch, linearized dynamics in turn implies separabil-
ity of the s and the u degrees of freedom, i. e. , we may
write
provided ¢ itself is separable at t =0. Given significant
displacement (or energy) in the s mode, the overlap
(¢ I ¢(t» will be nearly zero unless ¢.(t) is in the
vicinity of ¢, i. e., once each period in the s motion,
when (¢. I ¢.(t» is large. For the brief period that this
overlap is large, the total overlap is modulated by
(¢u I ¢u(t». It is evidently important to know this over-
lap only for a short time once each period in the s mo-
tion. This leads to the idea of looking at the u motion
in "stroboscopic" fashion once each time (¢s I ¢.(t» is
large, which in turn is closely related to the classical
idea of the Poincare surface of section discussed in Sec.
II. Given the Hamiltonian
H =t p; + t p; + V(s, u) , (3.2a)
where
V(s, u) = V(s, -u)
(Le., s is a symmetric coordinate) the separable s mo-
tion is clearly governed by
while the u motion in the separable approximation is
governed by the time dependent Hamiltonian
The requirement (3. 2b) together with the linearization
of the u motion leads to
where j is periodic with period 2rr /w s and time average
zero, w. is the period of the s motion for the given ini-
tial condition, and So is the maximum s displacement.
The requirement thatj(t) time average to zero implies
that Wu is in general a function of the energy in the s
oscillator. Equation (3.5) is an example of Hill's equa-
tion. 16
Since
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4729
the spectrum will be a convolution of the u and s spectra,
L e.,
(3.7a)
where
etc., andE 1u is the initial eigenvalue of the u oscillator.
Thus, we may consider the sand u spectra separately.
However, is just the Franck-Condon spectrum for
the potential V(s, 0) and the initial wave packet ¢ •.
Thus,
(3.8)
where
and
H. ¢n s =En• ¢n ••
(3.1)
Next the u spectra must be analyzed, and this is
where the "stroboscopic" approximation mentioned above
becomes useful. The strategy is to find an approximate
time independent effective Hamiltonian:JC for u motion
which can be quantized to give wave functions and ener-
gies which generate an approximate from which
the full spectrum can be derived via Eq. (3.7). Because
(¢ul¢u(t» is needed only at and near t=O, ± T., ± 2T.. ,
••• , the effect of :JC(t) on the history of the motion need
be examined only at these times, and since .JC(t) has
period T .. also, a great Simplification will result. We
study first the classical motion induced by :JC(t) and its
effect at time 0, ± T., .... The quantization will follow
immediately because :JC(t) is a quadratic function of Pu
andu.
Since JC(t) is a quadratic at all times, the values Pu(t)
(3.2b) and u(t) will be linear functions of Pu(O), u(O), and in
particular at t n; nTs' n '" 0, ± 1, ... , we have
(3.9)
(3.3)
where M n is the nth power of matrix M, which is a lin-
ear mapping2° of the (u, Pu) plane into itself. It must
also be area preserving. Since JC has period T .. the
(3.4)
dynamics repeats itself each successive period with the
result that the same mapping M applies each time a new
multiple of T. is reached. The area preserving nature
of the mapping implies det M =1. Repeated application
(3.5)
of M to a given (u, Pu) initial condition generates char-
acteristic invariant curves in the (u, Pu) plane along
which the mapped point must lie. In the case that the
mapping M is stable, its eigenvalues iJ.% are complex and
of unit modulus, i. e. ,
(3.10)
where v is real, and TrM is the trace of M. (Thus, in
the stable case, I TrM I < 2). It is easy to show that the
invariant curves in the stable case are ellipses in the
(3.6) (u, Pu) plane which in general, have major-minor axes
 4730 Heller, Stechel, and Davis: Molecular spectra
UNSTABLE
Pi.!
. U
actual .:. u'
linearized
eff
V
u' u'
FIG. 8. Typical surface of section invariant curves for the
stable (left-hand side) and unstable cases. Below each is shown
the corresponding effective potential.
not coinciding with the (u, Pu) axes. This is seen in
Figs. 1 and 8 at the lowest energy, where the invariant
curves are nearly elliptical (not quite exactly since the
fully coupled, not the linearized, equations of motion
were integrated). The parameters of the ellipses can
be expressed in terms of the matrix elements of M, but
the formulas are not especially illuminating.
The important point is that the invariant curves are
phase space orbits of an effective (u, Pu) Hamiltonian JC.
This Hamiltonian is a quadratic function of u and Pu,
thus the elliptical paths. The phase space trajectories
corresponding to JC not only lie on the invariant curves
generated by M, they have a period such that in the time
i . between successive mappings, JC carries the point
(Pu(O),u(O» into the same point (Pu(i.),U(i.», as M does.
However, the fact that the eigenvectors of M acquire
phase of ± v after time i. necessarily implies
(3.11)
where k is an integer and where nu is the frequency of
the periodic motion under JC. The stability parameter v
is easy to obtain (see below), therefore the frequency
nu is readily available.
It may seem that we have lost sight of the quantum
mechanics of u motion, but this is not so, due to the per-
fect correspondence of classical and quantum dynamics
for harmonic Hamiltonians 21 (even if time varying) such
as that governing the u motion, Eq. (3.5). In Appendix
A it is shown that the propagator U(i., 0) which propa-
gates <p, i. e.,
(3. 12),.
can be written
(3.13)
where Q is a quadratic form in u'P u ' Evidently, at
time i., we have
i. e.,
(3.14)
where JC is again the time independent effective Hamil-
tonian. Finally, we invoke the stroboscopic approxima-
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tion: for times near 0, ±i., ±2i., etc., we have
(3.15)
This is exact only at tn =ni•• but to the extent that the s
overlap is peaked about these values, Eq. (3.15) is a
valid approximation.
B. Stable case
Now we can take advantage of the time independent ef-
fective Hamiltonian JC. Clearly, its quantized energy
spectrum reads
(3.16)
Thus nut through v [Eq. (a.11)] and M [Eq. (3.10)], will
determine the position of the combination bands relative
to the pure symmetric stretch overtones.
Equally important are the Franck-Condon factors.
These must be given by
(a.17)
where
JCcf>n =Enucf>n
In Appendix B some properties of the cf>n's and their
Franck-Condon overlaps fnu are derived. It is evident
that <Pu cannot be orthogonal to a typical cf>., for the latter
are eigenfunctions of a Hamiltonian JC with invariant
curves which are not symmetric with respect to the u
axis, i. e., JC contains a term involving the product
Pu' u. If <P0 u is the ground state of the uncoupled u oscil-
lator, then typically fnu = 1<<P0 u 1cf>n> 12 will satisfy
fou:S 1 , (3. 18a)
while
o <flu «fo u ' (3. 18b)
o < f2 u «flu' etc. (a. 18c)
The Franck-Condon factors fnu' n 2: 1, give rise to com-
bination lines in·the spectrum: we have
(3. 19)
and [see Eqs. (3.7) and (a.8)]
For example, suppose En =(n.+t)w., w.=2.0, nu =1.1,
• a line (2,0) of strength
E j =tw., and E j =tnu. Then
8 u
f2s fou corresponding to n. =2, nu = 0, appears at w =4.0,
while the combination (1,2) appears with reduced
strength f1. f2 u at w =4.2. Sincefnu>O, n even, the combi-
nations cannot have zero intensity, unless the s -u cou-
pling is removed. By changing <Pu, the fnu can be mini-
mized, but there will always be a residual intensity
which is due to dynamiC, anharmonic coupling. This re-
sidual intensity is expected to grow as the unstable re-
gion is approached. This occurs because JC rotates its
axes further away from the u,Pu axes and nu deviates
further and further from the ull;coupled frequency wu'
Both of these factors tend to increase Franck-Condon
intensity in the combinations.
 Heller, Stechel, and Davis: Molecular spectra
The spacing of the lines and the approach to instability
is a most intriguing question. To answer it properly,
we must address a slightly subtle point. The semiclas-
sical approximations we have introduced (linearized dy-
namics, stroboscopic effective JC) give rise to the entire
Franck-Condon spectrum, via Eqs. (2.4), (3.6), (3.7),
and (3.20). However, the question arises as to the
choice of the "central" trajectory in phase space about
which the dynamics is linearized, giving rise to the ef-
fective JC. Often, this point would correspond to the
average position and momentum of cP. However, the
linearization is most accurate near the phase space do-
main of the central trajectory, and thus it follows that
the predicted spectrum is most accurate near the energy
of the central trajectory. Therefore, to examine the
question of the spacing of the combination overtone pairs,
we determine the classical stability parameter v (and
thus !1 u ) as a function of energy as we move through the
Franck-Condon envelope. [The sign of v and value of
the integer appearing in Eq. (3.11) are chosen so as to
give the correct value for !1 u in the uncoupled case. 1
The dashed lines in Fig. 6 show, in the stable region,
the value of v'" vlrr as a function of position in the
(2q la, Ja) plane. Although Fig. 6 is special to the
Mathieu equation, the behavior as resonance is ap-
proached is generic: v approaches 1 or 0, and as a re-
sult !1 u - pw., where p is an integer or half-integer, ac-
cording to the order of the resonance. For example, if
Ja = 1.1, then p = t. As a result, the combination lines
get closer to their neighboring parent pure overtone
lines as resonance is approached. This occurs because,
for example, as !1 u - tw.,the line (n., 0) coincides with
(n s -1, 2), whereas at lower energy [say the (2,0) and
(1,2) pair 1the splitting was - O. 2. Figure 6 shows that
if the frequencies are such as to be on the "low side" of
a resonance (for example, ra
= 1. 9) then as E (thus q) is
increased, v is not monotonic. This allows for some
splitting apart of the combination-overtone pairs before
they again approach each other closer to resonance.
Moreover, on all the low sides (2w u cS mw s )m=1,2, •••
resonance is harder to reach (see Figs. 6 and 7) as men-
tioned earlier.
The trends predicted above are observed in practice,
at least qualitatively. Table I and Fig. 1 show the "pre-
resonant attraction" of quasidegenerate levels as pre-
dicted above, although the spacing does not actually
reach zero as resonance is approached. Also seen in
Fig. 1 is the growth of the combination intensities as
resonance is approached. Detailed calculations have
confirmed the high side vs low side stability effects re-
ferred to above and shown in Fig. 7 (see the conclusion).
To recapitulate,
The pre resonant region is characterized by low
combination band intensity, and combination-over-
tone pairs which attract each other relative to
their uncoupled positions. Some cases may show
preresonant repulsion of levels. As resonance
is approached, the combinations grow in intensity
and the tendency toward attraction increases. It
it easier to reach resonance from the "high side"
(2w u?: mw.) than the "low side" (2wucS mw s ), es-
pecially in the 1: 1 and 3: 2 cases.
J. Chern. Phys., Vol. 73, No. 10, 15 November 1980
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4731
Before examining the unstable case, we note that the
predicted u-mode spacings [Eq. (3.16)1 are not correct
even in the limiting case of an uncoupled anharmonic
oscillator in u and s. 18 However, the higher overtones
of u motion, where the error is worst, do not appear
with measureable intensity in the spectrum. The effec-
tive frequency !1 u is most valid for the lowest u-mode
overtones. Thus, when the factor of intensity is weighed
in, which we have been able to do through the introduc-
tion of JC, the physical meaning of the stability parameter
analysis of periodic orbits 7c,d,17-19 becomes clearer.
c. Unstable case
In the preresonant, stable case we learn to interpret
the elliptical invariant curves as those of an effective JC,
whose frequency !1 u and eigenfunctions <Pn determine the
combination band spectrum. The same holds true above
resonance, although JC corresponds to an inverted har-
monic oscillator (see Fig. 8), and indeed the eigenvalues
of M are now real and of the form
Jl±=e·iv , (3.21a)
where v is pure imaginary. Then
and !1 u is also pure imaginary. The eigenvalues of JC
thus form a continuum Eku and the eigenvectors <Pk sig-
nificantly overlap cPu over a range of k values, giving
rise to a broadened band for :6 u (w). Since we are deal-
ing with a bound potential, the true spectrum is of
course discreet, and the broadened band results from
linearization of the dynamics in our semiclassical ap-
proximation: The semiclassical spectrum "thinks" the
effective potential is globally an inverted barrier, where-
as it is really only locally so, as suggested by the
double well effective potential shown in Fig. 8:
In prac-
tice, it is found that the continuous band :6 u (w) in the
resonant region closely follows a true envelope of the
corresponding overtone -combination set of discrete
lines [belonging to a parent (n., 0) overtone 1seen in the
exact spectrum [see Fig. 5(c)1. This can be understood
as follows: The:6 u is given by Eq. (3.7b), which shows
that the lower resolution features come from shorter
times in cPu(t). This short time dynamics is given cor-
rectly by the inverted barrier approximation, so long as
cPu does not initially extend into the double well region.
At longer times, recurrences set in due to the double
well potential, giving rise to the spectral lines under
the envelope, but the linearized approximation misses
this and settles for the envelope itself.
More quantitatively, the parameter ru =i!1u gives the
bandwith of the envelope corresponding to each set of
discrete lines belonging to a parent (n., 0) overtone.
This is reasonable, since ru gives the exponential rate
at which trajectories leave the u =0 region, according
to Eqs. (3.21) and (3.9). Since the trajectories control
the wave packet cPu(t), it can be shown that for long
times I (cPul cPu(t) I goes as e- rut / 2 • One objection might
be that there must be some dependence on the nature of
the state cPu, and this is certainly true. However, calcula-
 4732 Heller, Stechel, and Davis: Molecular spectra

tions have shown that the width of the band is very close TABLE II. Fermi resonant band-
to ru over rather large variations in w when cPu takes the widths.
form (see Fig. 9) a ns b rue rd
EI'\>.
(3.22) 8.0 7 0.049 0.091
Moreover, if w < r u, the band is skewed to the low ener- 9.0 8 0.066 0.101
10.0 9 0.082 0.110
gy side, and if w > r u, the skewing is to the high e ne rgy 11.0 10 0.092 0.116
side (Fig. 9). 12.0 11 O. 103 0.126
Since the rate of escape, and thus r u , increases as the aEnergy of the maximum in the
the unstable region (shaded areas in Figs. 6 and 7, for smoothed absorption band.
example) is penetrated further, the generic behavior b ns is the symmetric stretch assign-

will be increasing band widths with increasing energy.
However, the bandwidths may not depend linearly on the
energy or may not be a monotonic function of the en-I
ergy, since the r u depends also on how w sand Wu vary
with total energy in the s mode. It is possible, for
strong "diagonal" anharmonicity, to carry the s-u
modes out of resonance as energy is increased.
In practice the matrix M (and thus Ou or ru) is easily
determined by the method of Greene. 22 This method re-
quires running two trajectories in the vicinity of the
central trajectory, for one period T •• These three tra-
jectories are sufficient to determine M. The same tra-
jectories are used in the cluster method. 13 Table II
shows r u vs FWHM bandwidths for the resonant bands
in Fig. 1.
The unstable region can be designated the Fermi
FWHM=I.O
ment of the band, i. e., the band
arises out of the zero order (n s ' 0)
level.
er"= I v I /Ts. where Ts=27r in this
case and I v I is the stability param-
eter. determined at (E ..... -1. 05).
FWHM measured bandwidth for
the smooth fit to the spectral lines
obtained from a full semiclassical
wave bracket propagation and
Fourier transform of <¢ I cp(t).
See Fig. 5(c) and the discussion in
Sec. IID.
resonant region, for there is every reason to extend the
definition of Fermi resonance to include the post-reso-
nant, unstable behavior of the type we have just dis-
cussed. In the event that there is a preresonant region
in the spectrum, the Fermi resonance may set in without
any repulsion of zero order levels either above or below
resonance. Repulsion of levels seems to occur when
there is no pre resonant domain, and the first resonant
pair of levels are energetically in an unstable region;
in which case, they interact strongly and split apart.
An exception to this rule occurs for the "low side" pre-
resonant cases mentioned above, where the stability
parameter is not a monotonic function of energy.
Another exception occurs for the first isolated pair of
levels in the spectrum, if the levels are of the same
symmetry. Even in the stable regime, a slight splitting
but weak interaction will be noted for the first isolated
pair.

-5 -4 -3 -2 -I
IV. CONCLUSION
The connections between quantum spectral features
0·1.0 and wave functions on the one hand, and classical dy-
namics on the other, seem to be very close for the case
·······w·3.0
of an isolated resonance examined here. A complete
----w·0.25 picture has emerged, cemented by numerical and semi-

£
,1'·.
:\.
----FWHM-I.I classical evidence. Further, the notion of a Fermi
resonance has been augmented to include the possibility
': \'. ·······FWHM .. I.I
that two modes may not interact resonantly until midway
':
f:
\'.
\'. in a spectrum, and the spectral signatures of this effect
//: \ .... ha ve been identified. Earlier, 11 it was pointed out that
1-"""'1 .... / .' " •..... CO2 is very deep in the post-resonant region, both clas-
-5 -4 -3 -2 -I 0 1 2 3 4 5 6 sically and quantally, even at the lowest energies in the
E spectrum, as regards the symmetric stretch-bend inter-
action. However, the symmetric stretch-unsymmetric
FIG. 9. Broadened bands due to decay on an inve rted barrier.
The initial cp is given in Eq. (3.22), the potential is V(u) stretch interaction is pre-resonant until about 16500
= -! n2 u 2 with a corresponding r w of 1. 0 W = 1. 0). Note how cm- 1 total energy. (A better potential surface will be
insensitive the FWHM is to the form of cpo needed to firm up this latter estimate.) It will be very

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 Heller, Stechel, and Davis: Molecular spectra
interesting if spectra can be found which show directly
the transition from stable to unstable motion, not only
from the point of view of this work but also since it will
provide some evidence for the change from normal mode
behavior at low energies to energy redistribution at high-
er energies.
We believe the present work is the most explicit to
date regarding the interpretation of homogeneous spec-
tral bandwidths in terms of classical anharmonic motion
and rates of classical flow. Pending results of calcula-
tions on three or more dimensions now underway, the
evidence seems to point to a large future role for clas-
sical trajectory analysis of intramolecular energy flow
and spectral features.
It is quite possible for two modes to remain stable and
nonresonant until very high energies, due primarily to a
poor match of the uncoupled frequencies to any low order
resonant conditions. It remains possible in the absence
of any evidence to the contrary that Significant stable do-
mains can exist in the phase space of the molecule well
up into the mostly stochastic regimes and perhaps above
the dissociation energy of the molecule. Symmetric
stretch motion of the type we have been considering is
likely to be accessible experimentally. For example,
many electronic transitions involve large displacement
in the totally symmetric stretch coordinate. While
stable domains may occupy a small fraction of the phase
space of the molecule, their presence could significantly
affect the energy flow in such totally symmetric stretch
Franck-Condon spectra. The importance of stable
periodic "traps" in the phase space of the molecule at
high energy remains an important open question. It
seems likely that the volume of such phase space traps
must compare favorably with the appropriate power of
Planck's constant h, lest its effect be "washed out."
Many possible extensions of the present work remain
to be developed. A short list includes consideration of
nonsymmetric periodic trajectories, extension to sev-
eral dimensions, consideration of high order fixed
points of the motion, and obtaining spectra in the vicinity,
but not surrounding, periodic fixed points. It seems
that the present approach, which attempts to relate spec-
tral features at various levels of resolution with classi-
cal and quantum dynamics for correspondingly short (low
resolution) and long (high resolution) times, becomes in-
valuable when the molecules considered contain more
than three or four atoms. This is because individual
spectral lines are becoming unresolvable (and irrele-
vant) as densities of stat-es increase, and synthesizing
the experimental spectra by smoothing over resolved
ab initio calculations is no longer possible because far
too many states are involved. Clearly, some sort of
dynamic (time dependent) spectral analysis is required.
Even though the present work is couched mostly in the
language of two dimenSions, there is a broad class of
polyatomic systems for which the analysis carries over
directly. This includes the possibility that a symmetric
mode is excited, which then couples rapidly and strongly
into one other mode; subsequent decay into other degrees
of freedom will leave a spectrum very much like that
seen in Fig. 1, still very describable in terms of two
J. Chern. Phys., Vol. 73, No. 10, 15 November 1980
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4733
dominant modes. Another case that can be synthesized
from the presen t analysis is one symmetric mode cou-
pled to two or more other modes which do not couple
strongly with each other. Then we can write (in the
case of three modes)
(4.1)
and the full. spectrum would simply be a convolution of
three individual spectra, two of which arise from effec-
tive Hamiltonia Je1
We present a final example which seems to raise the
possibility of extreme sensitivity of molecular spectra,
wave functions, and energy transfer to details of the po-
tential surface. Figure 10 shows, at the top, two very
similar potential surfaces VI and VII, which have the
form
The uncoupled frequency WI is chosen to be 0.975, and
wlI is 1. 025. This gives"; a I = 2WI/ Ws = 1. 95, and van
=2WIJWs=2.05, where fa =2 is an exact 1:1 reso-
nance. Figures 6 and 7 show that VI is expected to be
more stable for a given energy than Vn, and the wave
functions 1f!i and 1f!iI shown in Fig. 10 confirm this effect.
The wave function 1f!I is the 109th eigenstate of VI' and
1f!1I is the 103rd eigenstate of Vn, and both have energies
EI'" Ell '" 14. Both 1f!I and 1f!n are wave functions which
possess the most symmetric stretch character near
E = 14, as evidenced by Franck-Condon factors with a
symmetrically displaced wave packet.
The classical trajectories (Mathieu equation in this
case) show that the symmetric stretch is stable for Vr.
but unstable for VII, near E =14. There is a corre-
sponding dramatic change in the wave functions, as seen
in Fig. 10. The sensitivity of the wave functions to a
small change in the potential surface evidenced here has
direct implications for energy exchange and the spec-
trum. The latter, of course, would show typical post-
resonant broadening for VII and preresonant weak inter-
actions for VI' A small (5%) change in a potential par-
ameter has resulted in qualitatively different behavior
for 1f!I and 1f!II' Such "bifurcations" are well studied in
classical mechanics,23 and this example shows that they
occur in quantum systems as well.
We have been able in this paper to provide a very
specific link between the phenomenology of isolated
classical resonances and the corresponding quantum
phenomenology. Because of the relative Simplicity of
isolated resonances, we have been much more specific
about the quantum-classical correspondences than has
been possible for the question of the onset of stochas-
ticity.l,2
In the case of an isolated resonance we have achieved
an understanding of certain spectral features in terms
of the underlying dynamics, even to the point of pre-
dicting bandwidths, overtone-combination spacings, and
intensities using classical input. This has been accom-
lished without any reference to quantization conditions
on nonseparable potential surfaces. In abandoning the
idea of predicting exact eigenvalues, we focus on dynam-
ical properties of potential surfaces, and we extract di-
 4734 Heller, Stechel, and Davis: Molecular spectra

FIG. 10. Potential contours for VI (above left) and VII (above right), and their corresponding wave functions at E = 14, as de-
scribed in text.

rectly the essential features leading to the observed
spectra. This approach will become a necessity in
dealing with "typical" polyatomics with vibrational densi-
ties of states from 10 to 10 14 per em-I. It has already
proven very useful in the theory of polyatomic photodis-
sociation spectra l2 and Raman spectra. 24
j(nl'). As 1'- 0, and n - 00, Eq. (A2) becomes exact.
However, from the Baker-Hausdorff theorem, 25 i. e. ,
e A e B =exp {(A +B +HA, Bl +MA, [A, BlJ + ft{[A , Bl,BJ, + ••• },
(A3)
it is easily shown that

(A4)
ACKNOWLEDGMENTS
where QIJ Qz, and Q3 are quadratic forms in Pu, u.
This work was supported by NSF Grant No. CHE77-
Successive application of Eq. (A4) to Eq. (A2) shows
13305.
(A5)
APPENDIX A where Q is again quadratic.
Suppose we approximate j(t) in Eq. (3.5) by piecewise
constant terms, of duration 1', i.e.,
(AI) APPENDIX B
where n =0, ± 1, ...• Then Here we derive the overlap between the ground state
rjJ0u of a harmonic oscillator and the state <Pn of another
rjJ(t) "" exp[ -iHn+l(t -nl')l 0 •• e- iH2T e- iH1T rjJ(O) =UT(t)rjJ(O) • harmonic oscillator whose major-minor axes u',
(A2) are rotated by an angle () from the u,Pu axes (see Fig.
Hn is the time independent quadratic Hamiltonian in the 8). First we require the amplitude between the posi-
nth time interval given by replacingj(t) in Eq. (3.5) by tion vectors in the two systems

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 Heller, Stechel, and Davis: Molecular spectra 4735

I
(u u') = (- cscB /21Ti) 11 2 Phys. A 10, 2083(1977); E. J. Heller, Chern. Phys. Lett. 60,
338 (1979); R. M. Stratt, N. C. Handy, and W. H. Miller. J.
(B1) Chern. Phys. 71, 3311 (1979); E. J. Heller. ibid. 72, 1337
(1980) .
which can easily be derived from the generating function 3B . V. Chirikov, Research Concerning the Theory of Non-
for the (u,Pu)- (u', transformation. 26 Then we have linear Resonance and Stochasticity, translated as CERN 71-40,
Geneva (1971); D. W. Oxtoby and S. A. Rice, J. Chern. Phys.
(<bOu!$n)= f dudu'(<bouiu)(ulu')(u' $n) , I (B2) 65, 1676 (1976).
4See , e.g., J. Ford, Adv. Chern. Phys. 24, 155 (1973); in
where Fundamental Problems in Statistical Mechanics, edited by
E. D. G. Cohen (North-Holland, Amsterdam, 1975), Vol. 3,
(<boul u ) = (W u/1T)1/4 e -<wu/2)u2 , (B3a) p. 215.
5G. Herzberg, Infrared and Raman SPectra of Polyatomic Mole-
(u 'I $n)-(
- 2nn! n:rr e -<ou/2)u'2Hn("'"
V nu u
') . (B3b) cules (Van Nostrand, New York, 1945), p. 215.
6M. J. Davis and E. J. Heller, J. Chern. Phys. 71, 3383
We can now perform the du integral in (B2) to give (1979).
7(a) D. W. Noid, M. L. Koszykowski, and R. A. Marcus, J.

(<boJ $n) =C 1 f /
du ' e- C2U'2 Hn(ffiuu ) , (B4)
Chern. Phys. 67. 2864 (1979); (b) D. W. Noid and R. A.
Marcus, ibid. 62, 2119 (1975); (c) R. A. Marcus, Faraday
Discuss. Chern. Soc. 55. 9 (1973); (d) W. Eastes and R. A.
where Marcus, J. Chern. Phys. 61, 430 (1974).
81. C. PerCival, J. Phys. A 7, 794 (1974); Adv. Chern. Phys.
C .fw.If:. )112 (
=(....:...=.JC.:. 2 ) 1/2 36. 1 (1977).
1 2nn!n: wu+icotB 9N. C. Handy, S. M. Colwell, and H. W. Miller, Faraday
Discuss. Chern. Soc. 62. 29 (1977).
and
S. Sorbie and N. C. Handy, Mol. Phys. 33, 1319 (1977).
2
c = CSC 0 i to nu "E. J. Heller, E. B. Stechel, and M. J. Davis, J. Chern.
2 2w u + 2i cotO + 2" co +""2' Phys. 71, 4759 (1979).
12E. J. Heller, J. Chern. Phys. 68, 2066 (1978); 68, 38!n
Next we employ the generating function for H u , namely, (1978) .
13 E • J. Heller, J. Chern. Phys. 65, 4979 (1976); K. C. Kulan-
:!Hn(x-) , (B5) der and E. J. Heller, ibid. 69. 2439 (1978).
14See D. W. Noid, M. L. Koszykowski, and R. A. Marcus
[J. Chern. Phys. 67, 404 (1977)] for a method for obtaining
to finally obtain
"spectra" frorn trajectories. See also K. D. Hansel, Chern.
( (1T )1/2 ,..,,12 n! ( 1)n12 (n even) , Phys. 33. 35 (1978); Chern. Phys. Lett. 57, 619 (1978).
(<bo J$n>=I:1 C2 '-'3 (n!2)!- 15E . Thiele and D. J. Wilson. J. Chern. Phys. 35, 1256 (1961).
16W . J. Cunningham, Introduction to Non-Linear Analysis
(n odd) , (McGraw-Hill, New York. 1958), Chaps. 9 and 10.
(B6) 17(a) M. C. Gutzwiller, J. Math. Phys. 12, 343 (1971); (b) w.
where H. Miller, J. Chern. Phys. 56, 38 (1972).
18W . H. Miller. J. Chern. Phys. 63, 996 (1975).
C3 =(1 + n /c2 )
U
• 19M . V. Berry and M. Tabor, Proc. R. Soc. London Ser. A
349. 101 (1976).
Note that the odd states (n =odd) are thus missing in the 20Se e M. V. Berry, N. L. Balazs, M. Tabor, and A. Voros
spectrum, as must be true. [Ann. Phys. (N. Y.) 122,26 (1979)] for a discussion of one-
dirnensional quantum maps. Our quantum mapping is some-
what different in that it arises out of a surface of section.
See also G. Gasati, B. V. Chirikov. F. M. Izraelev, and J.
I For recent reviews, see S. A. Rice, inAdvances in Laser Ford, in Lecture Notes in Physics. Vol. 93 (Springer, 1979).
Chemistry, edited by A. Zewail (Springer, New York, 1978); 21 See , e.g., E. J. Heller, J. Chern. Phys. 62, 1544 (1975);
and P. Brumer, in Advances in Chemical Physics, edited by 65, 1289 (1976).
S. A. Rice (John Wiley, New York), to be published. 22J. M. Greene, J. Math. Phys. 9, 760 (1969).
2See P. Pechukas, J. Chern. Phys. 57, 5577 (1972); K. S. J. 23A . Abraham and J. E. Marsden, Foundations of Mechanics,
Nordholrn and S. A. Rice, ibid. 61, 203 (1974); 61, 768 (1974); 2nd ed. (Benjamin Cummings, Reading, Mass .• 1979).
I. C. Percival, J. Phys. A 7, 794 (1974); I. C. Percival and 24Soo_Y. Lee and E. J. Heller, J. Chern. Phys. 71, 4777
N. Pornpherey, J. Phys. B 31. 97 (1976); N. Pornpherey, J. (1979).
Phys. B 7. 1909 (1974); W. H. Miller, J. Chern. Phys. (1976); 25See. e.g., R. M. Wilcox, J. Math. Phys. 8, 962 (1967).
(1976); N. Pornpherey, J. Phys. B 7. 1909 (1974); W. H. 26See , e.g., W. H. Miller, J. Chern. Phys. 53, 1949 (1970);
Miller, J. Chern. Phys. 64, 2880 (1976); M. V. Berry, J. E. J. Heller, ibid. 66, 5777 (1977).

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