Quantum dynamics of the Henon–Heiles system

Mordechai Bixon and Joshua Jortner

Citation: The Journal of Chemical Physics 77, 4175 (1982); doi: 10.1063/1.444328
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 Quantum dynamics of the Henon-Heiles system
Mordechai Bixon and Joshua Jortner
Department a/Chemistry. Tel-Aviv University. Tel Aviv. Israel
(Received 11 August 1981; accepted 26 October 1981)

In this paper, we investigate the quantum dynamics of wave packets of bound states in the nonlin~ar
Henon-Heiles (HH) system. The time evolution of a wave packet was separated into two processes. involving
(al the motion of its first moments and (b) its spreading. On the time scale when wave packet spreading can be
neglected, we were able to establish relations between wave packet quantum dynamics expressed in terms of
the initial-state population probability PIt) and classical trajectory dynamics. We have demonstrated that the
initial states, which are characterized by a periodic time evolution of P(t) over many periods, are related to the
five elliptic periodic orbits in the HH system. The decay of PIt) over a few vibrational periods is re~ted to the
classical features of quasiperiodic trajectories and can be accounted for in terms of overlap reduction effects.
When the center of the initial wave packet is moved further away from the classical periodic orbits, PIt) is
characterized by a single initial peak followed by a "noisy" background. There is no qualitative distinction
between the "short-time" behavior of a wave packet initiated in distant integrable regions and in classical
stochastic regions. For long times, wave packet spreading effects set in. Quantum mechanical estimates for the
spreading time T" which depends on the initial conditions, were provided. For wave ~ckets initiated on
periodic trajectories, T, is very long, becoming shorter as one moves away from the fixed pOints. The qua.ntu.m
mechanical long time (t>T,) behavior of PIt) exhibits small-amplitude noisy time dependence for all initial
conditions. This behavior may be described as "quantum mechanical stochasticity" and is related to the
universal feature of irregularity of the spectral resolution of all wave packets in a nonlinear system. From this
point of view, all wave packets exhibit "quantum stochastic behavior," but there are vast quantitative
differences for different initial conditions that are manifested in terms of the values of T, and of the average
noisy amplitude. It should be emphasized that this "quantum stochasticity" is not related to classical
stochasticity phenomena.

I. INTRODUCTION decay of quantum wave packets bears an analogy to clas-

Theoretical research in the area of intramolecular
vibrational energy flow in poly atomic molecules l - 3 was
motivated by advances in claSSical mechanics of nonlin-
ear coupled systems, which established the existence
of an onset for stochastic behavior. 4- 12 The possible
implications of classical stochastic phenomena in quan-
tum systems are of conSiderable methodological and
practical interest_ 13-37 Studies of the consequences of
quantum stochasticity were concerned with the energy
spectrum, 18.25-33 the nature of the wave func-
tions, 14-16.23.24 and the transition moments. 16.20.28-30
Recent studies of these problems went beyond the prop-
erties of stationary states to explore the dynamics of
metastable wave packets of bound states, 32.34-37 which
constitute the quantum mechanical analog of classical
trajectories. Two limiting types of the time evolution
of initially coherent Gaussian wave packets in the bound
level structure of the nonlinear and nonintegrable Henon-
Heiles32.34-36 and the Barbanis 34 systems were estab-
lished. One limit involves periodic (or quasiperiodic)
time evolution, while the other manifests rapid decay
of the initial state population probability of the wave
packet. These two limiting forms of wave packet dy-
namics peacefully coexist, the specific form of the time
evolution being determined by the initial conditions.
These novel features of wave packet dynamics raise
some intriguing questions: (a) Can one establish a cor-
respondence between classical phenomena of trajectory
dynamics and the quantum dynamics of wave packets?
In this context, two questions Should be raised. First,
we should inquire whether one can find a classical anal-
ogy for the quasiperiodic quantum time evolution. Sec-
ond, it would be intriguing to find out whether the rapid
sical chaotic behavior. (b) In a further pursuit of clas-
sical quantum analogies, it is interesting to inquire
further32.34.35 whether, on the basis of wave packet dy-
namics, one can establish a quantum-mechanical analog
for the classical "critical" energy4.5 for the "transi-
tion" from quasiperiodic to chaotic motion. (c) Are
there intrinsic quantum mechanical effects, originating
from interference phenomena reflected in the dynamics
of wave packets? (d) What effects revealed in the quan-
tum dynamics of wave packets reflect the nonseparabil-
ity of the potential? This question is of considerable
technical interest in the search for unique features of a
nonlinear nonseparable system. (e) Can one establish
a hierarchy of time scales for the characterization of
various classical and quantum effects that determine
wave packet dynamics? This issue is of practical in-
terest as intramolecular dynamics is in real life con-
cerned with finite time dynamics, the relevant upper
limit being established by radiative and collisional
damping phenomena.
In this paper, we consider the dynamics of wave
packets of bound states in the nonlinear Henon-Heiles
system. We shall attempt to explore the correspondence
between classical and quantum dynamics, attempting to
elucidate those features of the wave packet dynamics,
which have a direct classical analog, and those char-
acteristics originating from quantum phenomena. This
study will bear on the cardinal question of whether the
quantum dynamics of a wave packet reveals some fea-
tures of stochasticity phenomena and, more important,
to what extent are quantum stochasticity phenomena
relevant for the understanding of intramolecular dy-
namics in a bound level structure.

J. Chern. Phys. 77(7). 15 Oct. 1982 0021·9606/82/204175-13$02.10 © 1982 American Institute of Physics 4175

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 4176 M. Bixon and J. Jortner: Quantum dynamics of the Henon-Heiles system
II. EFFECTIVE POTENTIALS FOR WAVE PACKET
DYNAMICS
The dynamics of classical trajectories, investigated
in the phase space, is described in terms of the classi-
cal equations of motion for the coordinates and mo-
menta. The quantum analog of a classical trajectory
is a wave packet lJ!(t). Ehrenfest's equations 38 for the
quantum mechanical averages of the coordinates and
momenta of the wave packet constitute the quantum
analog of the classical equations of motion. Consider
a system with n degrees of freedom specified by the
Hamiltonian
where Pi and qi (j =1,2' .. n) are the momentum and co-
ordinate operators, respectively, whose time-dependent
first moments are given by
(Pi) =(1J!(t) IPi IIJ!(t) ,
I
(q) = (1J!(t) qi IIJ!(t)
By Ehrenfest's theorem these moments satisfy the equa-
tions of motion:
:t (Pi) = -(:~) ,
where (0) =(W) I OIIJ!(t) for any operator O.
As is well known, for a harmonic potential,
V=~h~/2) and «w/aqi) =(qi)' whereupon the system
of the Ehrenfest equations is closed in the first mo-
ments, being isomorphous with Newton's classical
equations of motion for this system. This simple re-
sult breaks down for nonharmonic potentials. Disper-
sion of the wave packet in a nonharmonic potential will
result in deviations of the quantum-mechanical equations
of motion, Eq. (II.3), from the classical Hamiltonian
equations. We shall attempt to advance a qualitative
description of the quantum-mechanical dispersion of
wave packets, which will provide an insight into the
nature of quantum-mechanical dispersion phenomena
in nonharmonic potentials.
In the present work, we shall explicitly consider the
Henon-Heiles (HH) potentia1 39
V(ql' q2) =1 q~ +1 q~ +E(q~q2 - tq~)
In this case, one obtains
The higher order moments can be expressed in terms
of averages and variances as follows:
(qlq~=(ql)(q~+X12(t) ,
(qf) - (q~ =(ql)2 - (q~2 + Xll(t) - Xaa(t) ,
where
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Xla(t) =«ql - (ql») (qa -(q~» ,
Xll(t) =«ql -(ql»)2) , (n.9)
X22(t) =«qa - (q~)2)
The equation of motion takes the form
da
m dj! (ql) =(ql) + 2E (ql) (q~ + 2EXla(t) , (II. 10)
da
m dt a (q~ =(q~ H[ (ql)2 - (q~2] H[Xll(t) - Xaa(t) 1•
(II. 11)
From Eqs. (II. 10) and (11.11), it is apparent that the
quantum dynamics for an anharmonic potential differs
(II. 1) from the classical equations of motion, in view of the
appearance of the Xli(t) functions. The quantum equa-
tions of motion are isomorphous to the classical equa-
tions of motion in the effective potential
V(.l •• a.t) =(q~/2) + (qV2) + E(qfqa - tq~)
+ 2E {x12(t) ql + [Xll(t) - Xaa(t)]qa} , (n. 12)
(II. 2)
which, of course, differs from the potential V(ql,qa),
Eq. (II.4).
The functions Xli(t), appearing in Eq. (II. 12), depend
on the explicit form of the wave packet lJ!(t). Further-
more, these functions are time-dependent, reflecting
(II. 3)
the spread of the wave packet. On the time scale, when
the time variation of Xij(t) is slow relative to the time
evolution of the moments given by Eq. (II.2), specifying
the motion of the particle, one can take X/j(t) =Xli(O).
The quantum dynamics is then described by the conser-
vative effective potential
V(.l'.a' O) =V(ql,qa) + 2E hla(O)ql + [Xll(O) -X2a(0)]qa} ,
(II. 13)
where the last term in Eq. (II. 13) can be considered as
a quantum deformation of the classical potential. This
picture is applicable only on the relatively short-time
scale, as the time dependence of X/j(t) for longer times
has to be incorporated and the effective potential, Eq.
(n.12), is nonconservative.
Provided that the initial wave packet IJ!(O) in the HH
potential is spherically symmetrical, as is the case for
a (harmonic oscillator) coherent-state Gaussian wave
packet, one has
Xla(O) =0 ,
(II. 4) (n.14)
Xll(O) =Xaa(O)
In such case, the contribution of the higher moments
(II. 5) Xli(O) to the quantum deformation vanishes. Therefore,
the correction term in Eq. (II. 13) vanishes and
V(ql' qa, 0) =V(ql' qa)·
(II. 6)
Accordingly, in this case, the initial quantum dynam-
ics is isomorphous to the classical motion. We con-
clude that the HH model has the special property of its
Ehrenfest's equations for spherical symmetrical wave
(II. 7) packets, being initially equivalent to the classical
equations of motion. In this respect, the short-time
(II. 8)
behavior of the HH system is similar to the harmonic
motion, but differs from that of other nonlinear poten-
 M. Bixon and J. Jortner: Quantum dynamics of the Henon-Heiles system 4177

tials, such as the Barbanis system, where quantum

deformation effects are expected to be initially ex-
hibited.
From the foregoing discussion, it is apparent that the
solution of the classical equations of motion for the HH
system should be directly applicable for the utilization
of classical trajectory dynamics for the analysis of its
quantum-mechanical dynamics, on a time scale where
the effects of the spreading of the wave packets are
negligible. There exists a large bulk of work on the
qualitative properties of the classical HH model, and
on the numerical integration of the classical equations
of motion. In Appendix A and in Figs. 1 and 2, we have
reviewed some of these classical results, which are
relevant for our discussion. In the next section, we
shall proceed to establish the correspondence between
quantum dynamics of wave packets and classical trajec-
tory dynamics.

III. CLASSICAL ANALOGS OF QUANTUM WAVE

PACKET DYNAMICS
General information concerning the quantum dynam-
ics of a wave packet is obtained from the initial popula-
tion probability32. 34-37
P(t) = 1(lJI(t) IIJI(O) 12 ,
i. e., the time dependent overlap between the wave
packet and its initial state, which was also referred to
as the survival probability. 37
The time evolution of a quantum-mechanical wave
packet can be described by (a) the motion of its average
position, which is given by the first moments (qj) and
(Pj), and (b) the spreading of the wave packet, de-
scribed to first order in terms of the second moments
XiJ(t). When the spreading [effect (b)] is appreciable,
the behavior of the average position [effect (a)] loses its
Significance for the characterization of the state of the
FIG. 1. The eight simple periodic orbits in the classical
Henon-Heiles system (Ref. 12). The orbits IT J <i=1,2,3,7,8)
are stable elliptic orbits which survive at all energies. The
orbits IT. (k=4,5,6) are hyperbolic, around which chaotic tra-
jectories develop at higher energies.
FIG. 2. A classical Poincare section at the phase space in the
P2 x q2 plane (for qt =0 and E =constant). The elliptic periodic
orbits Il 2 , Il 3 , IT l , and ITa are represented by points, while ITt
corresponds to the perimeter of the classically-allowed re-
gion. The closed curves correspond to the section of invariant
(III. 1)
tori on which quasiperiodic trajectories are located.
wave packet. Thus, classical trajectory dynamics can
provide meaningful classical quantum analogs, only
provided that the spreading [effect (b)] is negligible.
We shall separate our discussion of the quantum-me-
chanical motion of an initially coherent Gaussian wave
packet3 2.34,37 into two stages. First, we shall consider
the dynamics under the assumption that the wave pack-
et is not spreading. Second, we shall consider the
quantum-mechanical spreading of the wave packet. In
what follows, we shall consider the first stage, while
the discussion of the second part will be presented in
Sec. VI, where we shall explore the implications of the
quantum-mechanical wave packet spreading effects.
As long as the spreading of the wave packet can be
disregarded, the equations of motion for the HH system
are equivalent to the classical equations with the effec-
tive potential (11.13), which for a symmetric wave pack-
et reduce, according to Eq. (11.14), to the classical
equations of motion. For the time evolution of a non-
spreading coherent Gaussian wave packet, with which
we shall be concerned, we can use all the classical re-
sults (Appendix A) to account for time evolution of the
(nonspreading) wave packet in terms of classical tra-
jectory dynamics. In order to utilize the classical in-
formation regarding trajectory dynamics, let us define
a classical trajectory overlap integral P co(t). It is ex-
pressed in terms of the initial state population proba-
bility of a coherent Gaussian wave packet, which does
not change its shape, while its center moves along the
classical trajectory. Such a coherent wave packet is
characterized by the coordinates and momenta of its
center [q'(t), p'(t)] on the trajectory. This coherent
wave packet, expressed in terms of the appropriate re-

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 4178 M. Bixon and J. Jortner: Quantum dynamics of the Henon-Heiles system
duced variables, is taken in the following form:
Ij![ql q'(t) p'(t)]
=1T-1/4exp[_ [q-i'(t)]Z +i(P'(t). q_ p'(t)
(III. 2)
Now, q'(t) and p'(t) are taken to move according to the
classical equations of motion. The classical trajectory
overlap integral is defined as
depending only on the properties of the classical orbit.
As long as the spread of the quantum-mechanical wave
packet is negligible, we can identify Pco(t), Eq. (I1I.3),
with P(t), Eq. (III. 1). We shall now invoke the classi-
cal properties of fixed pOints and closed curves in the
Poincare sections (Appendix A) to gain information con-
cerning the properties of P co(t), thus elucidating the
features of P(t). Two situations will be considered:
(i) The wave packet is located initially on a fixed
point of the Poincare section, i. e., on a periodic orbit
n j U=1,2,3,7,8). After a single period, the wave
packet will return to the same point on the section. Ac-
cordingly, for a wave packet initiated at a fixed point,
P co(t) is a periodic function of t with a constant ampli-
tude. The same behavior will be exhibited by P(t) ini-
tiated at a fixed point, as long as spreading of the wave
packet is negligible.
(ii) The wave packet is located initially on a closed
curve around a fixed point. The undeformed wave packet
will return to the Poincare section at a different point,
belonging to the same closed curve. The distance d
between the initial point at the closed curve, where the
wave packet was initiated, and the consecutive crossing
is determined by the rotation number NR and the cir-
cumference C of the closed curve, so that
The classical overlap Pco(t) , and its quantum-mechani-
cal counterpart P(t), will be reduced after the first
crossing of the section, being smaller than unity, and
may be quite small provided that d> 1. Thus, purely
classical effects of quasiperiodic motion will result in
the initial decay of P(t). As a quantitative description
of these classical effects in the HH potential is rather
difficult, it will be useful to consider first a soluble
system.
IV. DYNAMICS OF WAVE PACKETS IN A SEPARABLE
HARMONIC SYSTEM
In order to elucidate the effects of classical trajec-
tory dynamics on the decay of P(t), we shall digress to
consider the dynamics of a simple system of a two-di-
mensional harmonic oscillator. This analytical soluble
system is of interest because of four reasons. First,
in this harmonic system, no spread of the coherent wave
packet occurs, whereupon Pco(t) =P(t) and the classical
analog of coherent wave packet dynamics should be ap-
plicable to describe the quantum dynamics at all times.
Second, it will demonstrate the utility of the rotation
number in determining the wave packet dynamics of this
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bound system. Third, quantitative results for the de-
cay of P(t) in this simple system will be useful for the
understanding of more complicated systems, such as
~ q'(t))]. the HH model. Fourth, the study of a separable and
integrable system will provide a partial answer to the
technical question, namely, what effects of wave packet
dynamics manifest the nonseparability of the potential.
The separable problem of a two-dimensional harmonic
oscillatory can, of course, be considered as two one-
(III. 3) dimensional oscillators with frequencies WI and Wz, each
of which conserves energy separately. For methodologi-
cal reasons, we proceed to consider the four-dimen-
sional phase space and the Poincare (ql = 0, E = const)
section. The Poincare section is the q2 X P2 plane; it
has a fixed pointqz = 0; P2 = 0, which is surrounded by closed
ellipses (or circles when proper units are used). The
rotation number is given by N R = (w z/ WI - 1) and it is a
constant, being independent of the specific ellipse or
of the energy.
The initial coherent state, specified by [ql(O), PI(O),
q2(0), P2(0)], is given by
"'(0) = (1T(J (J. )11 2 exp {- [ql -ql(O)) _ [qg -q2(0)]2
'I' I 2 2(J~ 2a~
+ ~[Pt(O) ql + P2(0) q2 -t PI(O) ql(O) - t P2(0) q2(0))} ,
(IV. 1)
where the characteristic lengths are
fi ) 1/2
a=
( -- 'j=12 (IV. 2)
j mWj , "
and the initial energies of the two modes are
1
E j =-2-[P/W+ W j qj(0)2] ;
mj
j = 1,2. A straightforward calculation based on Eq.
(III. 1) gives the time dependent quantum-mechanical
(III. 4) overlap as
P(t) =exp[(~)[COS(Wlt) -1]J exp[(~)[COS(W2t) -1]l
(IV. 3)
Because of the separability of the potential, P(t) is
separable.
We shall now be concerned with the changes in be-
havior of P(t) as the rotation number N R = (wJ WI) - 1 is
varied. The follOwing features are of interest: (1)
When NR = 0, one obtains a perfectly periodic behavior
with maximum amplitude unity and a period of 21TWil.
(2) When N R "* 0, which corresponds to a quasiperiodic
motion and Lissajous-type orbits, one observes decay
in the amplitude of the consecutive peaks of P(t). (3)
For small differences between the two characteristic
frequencies, we set w2 = WI + Ii, where (Ii/w l )« 1, so
that the rotation number is very small. Under these
circumstances, we may expand the cosine in Eq. (IV. 3)
and obtain the amplitude Bm of the mth peak of P(t) in
the form
Bm = exp [- fi~~ e:~r m2] . (IV.4)
We can identify Bm with the value of the envelope func-
 M. Bixon and J. Jortner: Quantum dynamics of the Henon-Heiles system
tion B(t) of P(t) at the times t = 21Tm/ Wi' This envelope
function is defined accordingly as
B(t) = exp[ - t2/~] ,
where the decay time
T flY t
= (lIwJE 2)1/2 0- 1 = (lIwJE2)1/2 (NR. w1 1
will be referred to in Sec. V as the overlap reduction
time. Accordingly, the overlap exhibits a Gaussian
decay in time. Two conclusions emerge from Eq.
(IV. 5). First, the decay becomes more rapid with in-
creasing the radius of the closed curve on the section.
This radius of the closed curve is proportional to E~/2
while, according to Eq. (IV. 6), TflY will decrease with
increasing E 2 • Second, the decay becomes faster with
increasing the rotation number 15/Wi as TflY 0::. Nil. (4)
Other obvious general properties of P(t), Eq. (IV .1),
involve its quasiperiodicity (or periodicity). If NR. is
a rational number, i. e., NR. =s/r, where sand rare
integers, then P(t) becomes periodic with a period
21Tr/ Wi' Otherwise, p(t) is in general a quasiperiodic
function.
V. CLASSICAL EFFECTS ON DYNAMICS OF WAVE
PACKETS IN THE HENON-HEILES SYSTEM
The simple example of the dynamics of the two-di-
mensional, separable harmonic oscillator are relevant
for the elucidation of the features of nonseparable sys-
tems. From the point of view of general methodology,
it is apparent that decay of P(t) is exhibited in a separ-
able and integrable system. From the point of view of
manifestation of the classical effects on the time evolu-
tion, we were able to establish the Gaussian time evolu-
tion, Eqs. (IV.4)-(IV.6), for the initial decay of the
coherent wave packet, as well as to establish the long
time quasiperiodic behavior. While for harmonic poten-
tials no spreading of coherent wave packets is exhibited
and Pco(t) =P(t) for all t, for the case of the HH system
we can consider classical effects only by examining
P co(t). The general features of the behavior of P co(t)
for wave packets in the integrable region of the HH sys-
tem are qualitatively similar to those of the two-dimen-
sional harmonic oscillator. An important technical dif-
ference, which will complicate enormously any quantita-
tive calculations for the HH system, is that the rotation
number NR. depends on the distance from the fixed point
and on the energy. Furthermore, the closed curves on
the sections may have different shapes. Nevertheless,
the general qualitative features of P co(t) are quite clear.
When the initial position [q'(O), p'(O)] of the center of the
wave packet moves away from an elliptic fixed point,
the rotation number increases and Pco(t) decays, at
least for several periods. The decay becomes more
rapid as the center moves further from the fixed point.
We shall now proceed to examine semiquantitatively
the decay of classical overlap in the integrable regions
of the HH potential. We shall consider the amplitudes
Bm of the peaks of Pco(t) after m vibrational periods,
which provide the envelope function of pco(t). The dis-
tance d 1 between successive reiterates [for ql(t) =0 at
all t 1is given by
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4179
d~ = [p 1(1) - P 1(0)j2 +[p2(1) - P2(O)]2 + [q!(l) -q2(0)]!,
(V. 1)
where ql(l) = 0, q!(l), Pl(1), and P2(1) are the coordinates
(IV. 5)
and momenta after one period. d~ contains a contribu-
tion from the qaXPa plane, which can be apprOXimated
as
(IV. 6)
(V. 2)
where C denotes again the circumference of the closed
curve on the section. The second contribution to Eq.
(V.1) involves [Pl(1)-Pl(0)]2, which can be evaluated
from the values of pz and q2' together with the energy
conservation relation
E =2"1(2 Z)la E:3
Pl+Pa +2"Q2-'3Q2 •
This second contribution to Eq. (V .1) will not exceed
the first one. Accordingly, for the sake of a rough es-
timate, we shall disregard the second contribution and
set
(V.3)
The distance d"" after m reiterates, is approximately
given by
(V.4)
As the wave packet is Gaussian, one obtains for the
amplitude Bm of the mth peak
Bm = exp( - d!/2) (V. 5)
which, with the aid of Eqs. (V. 3) and (V. 4), assumes
the form
(V.6)
In a complete analogy to the harmonic case treated in
the previous section, we define an envelope function
B(t) whose value at the time 21Tm/w is equal to Bm. The
envelope function has the follOWing Gaussian time depen-
dence:
B(t) =exp(-t2!T!.) , (V.7)
where the overlap reduction time TOY for the wave packet
is defined by
21T
TOT = wNR.C (V.8)
When WT flY =CNR. -1, one expects Pco(t) to exhibit several
peaks. When WTOT « 1, only the initial peak in P co(t) will
survive.
The overlap reduction time TflY' Eq. (V. 8), provides
a semiquantitative measure of the decay of the initial
state population probability of a wave packet, which
originates from purely classical effects of trajectory
dynamics for quasiperiodic trajectories. The decay of
P co(t) and of P(t) originates from a gradual decrease in
the overlap due to the motion along the classical trajec-
tory, according to Eq. (III. 2). It shOUld be noted, how-
ever, that Pco(t) does not continue to decrease indefinite-
ly, which brings us to the discussion of recurrence ef-
fects.
An additional important characteristic of Pco(t) in-
volves its recurrence properties. An exact recurrence
 4180 M. Bixon and J. Jortner: Quantum dynamics of the Henon-Heiles system
(a)
1.0
-'-0
U
CL
0
•
Tw
( b)
1.0
--0
~
0
(e)
--0
1.0
~ chastic manner. P eo(t) should consist of a single initial
0
1.0 (d)
--
0
u classical quasiperiodic motion for large rotation num-
CL
0
FIG. 3. A schematic representation of the different modes of
the time evolution of the classical trajectory overlap integral
P ",,(t), Eq. (III.3). Curve (a) corresponds to an (undeformable)
wave packet whose center is initiated on a fixed point (periodic
orblt), which is periodic with a period T.,= 2rr/w. Curve (b)
corresponds to a wave packet initiated in the integrable region
on a closed curve (quasiperiodic trajectory) with a small rota-
tion number. The initial decay of the envelope is character-
ized by the over lap reduction time T"" and after a long time
Til. approximate recurrence is exhibited. Curve (cI corre-
sponds to a wave packet initiated in the integrable region on a
closed curve (quasiperiodic trajectory), far away from a fixed
point, being specified by a large rotation number. The initial
decay is fast and approximate recurrence is exhibited after long
time Til.' Curve (d) corresponds to a wave packet initiated in
the nonintegrable stochastic region, exhibiting initial fast de-
cay followed by a "noisy" background.
time for the classical wave packet will exist if the rota-
tion number is rational, i. e., Nil. =sir, where sand r
are integers and the recurrence time is 211rlw. When
Nil. is not a rational number, one can define an approxi-
mate recurrence time 7"11., for which Peo(t) regains a
value close to unity. Obviously, 7"1/, has to be some
multiple of the inverse rotation number
7"1/, = 211MlwN1/, ,
where M is a large number.
In Fig. 3, we summarize the different modes of time
evolution of P eo(t) in the integrable regions of the HH
system. Three different time scales are exhibited that
characterize the classical behavior, i. e., the intra-
mode period 7"., = 2111 w, the overlap reduction time 7" fi'I'
Eq. (V.8), and the approximate recurrence time 7"1/,'
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When the rotation number increases as one moves away
from the fixed point, the initial classical decay of the
wave packet is exceedingly fast, retaining only the first
peak, while only after a long time a recurrence effect
will result in the resurrection of P eo(t). The short-
time features of P eo(t) are expected to be manifested in
the quantum-mechanical P(t), as they are usually ex-
hibited on the time scale, when the spreading of the
wave packet is insignificant. The classical approxi-
mate recurrence phenomena may be eroded by the
spreading of the quantum-mechanical wave packet.
Up to this point, our discussion was limited to the in-
tegrable regions of the classical phase space, which is
composed of invariant two-dimensional tori. In the
stochastic region of the classical phase space the situa-
tion is different, as each phase-space point is wander-
ing around, and its reiterates fill the region in a sto-
peak and subsequently decay to low values, while at
longer times some small uncorrelated peaks will be ex-
hibited in an irregular manner (Fig. 3). This behavior
of Peo(t) in the chaotic regime is qualitatively very sim-
ilar to the features of P eo(t) in the integrable region, for
N1/,C» 1 and when t<7"1/,. The only difference between
bers and chaotic motion is the approximate recurrence
exhibited in the former case. This approximate recur-
rence effect in the quasiperiodic motion may be eroded by
quantum-mechanical interference effects due to the
spread of the wave packet. One should bear in mind
that the discussion in the present section, which iden-
tifies P(t) with P eo(t) , is valid only provided that the
wave packet does not spread. This restriction will be
relaxed in the next section, where we shall discuss the
basic effects of quantum-mechanical spreading of the
wave packet.
VI. QUANTUM-MECHANICAL DEPHASING AND
SPREADING
The complete quantum-mechanical description of
wave packet dynamics starts from the conventional de-
scription of the wave packet
lji(t) =1: An In) exp( - iEntln) (VI. 1)
n
being expressed in terms of the eigenstates {I n)}, the
corresponding eigenvalues {En}' and the preparation
amplitudes {An}, which specify the initial condition, and
which satisfy the normalization condition
(VI. 2)
(V.9)
It is important to emphasize the obvious properties,
where only a finite number of eigenstates contribute to
the wave packet dynamics at all times, that the time
evolution of the wave packet spans only those eigenstates
which were initially populated, and that the populations
I <n Ilji(t) 12 =1An 12 of the initially populated eigenstates
are independent of time. The initial state population
probability is
 M. Bixon and J. Jortner: Quantum dynamics of the Henon-Heiles system
P(t) =14= IAII12 exp( - iEII/lrf
=L ~ IAII12IA".1 2exP(i(En -En,)t/Ir] , (VI. 3)
n n
being a Fourier sum with a large number of frequencies.
We shall now focus attention on the features of P(t)
with gradual increase of the time scale. Let us first
consider the features of the Fourier sum (VI. 3) at very
short times t ';'Ir/I En - En' I for all n, n', when the de-
tails of the energetic structure can be disregarded.
pet) will exhibit an initial decay, which corresponds to
the dephasing of the initial wave packet. The dephasing
time TD is given by the reciprocal of the energy spread
r of the wave packet
This is a well-known quantum-mechanical result, which
can be analytically derived for idealized ladder models,
where the dephasing is strictly exponential, and is borne
out by numerical simulations for other level structures,
e. g., random coupling and random spacing models,
where the decay is close to, but not strictly, exponen-
tial. The quantum-mechanical dephasing time TD [Eq.
(VI. 4)] has a clear classical analog. It can be described
as the time needed for the wave packet to move a dis-
tance equal to its width, i. e., TD '" a/v, where a is the
wave packet width and v =p/m is its velocity. The
width of a coherent wave packet is given by Eq. (IV. 2),
a'" (lr/mw)1/2, from which one obtains for the classical
description
TD"" am/p = (lr/mw)1/2(m/p) = (l/v2wH2m1i"w/p2)1/ 2
comparing the classical result Eq. (VI. 5) with the
quantum-mechanical dephasing time, Eq. (VI.4), one
obtains the reasonable result for the width of the wave
packet
.L)1/2
r""lrw ( 2mlrw '
which can be expressed in terms of the energy E of the
wave packet
rr:::lrw(E/lrw)1/2.
We now proceed to consider the quantum dynamics at
somewhat longer times t> TD , where the details of the
spectrum of the wave packet become pertinent. Equa-
tion (VI. 3) constitutes a quasiperiodic function of time,
which is composed of a large number of independent
frequencies. This basic feature of quantum dynamics
is different from the classical quasiperiodic motion on
the two-dimensional torous, which involves only two
frequencies. In this sense, the time development of
the quantum wave packet is qualitatively different from
that of a classical trajectory. The existence of a large
number of independent frequencies in the spectral reso-
lution of the wave packet is the mathematical manifesta-
tion of the spreading of the wave packet. Still, this
situation does not spoil the Similarity between P co(t)
and pet) for short times. For example, if the devia-
tions of all the frequencies from two basic frequencies
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4181
are small, then their effect will be manifested only after
a long time. A different relevant situation is encoun-
tered when the amplitudes of all those components,
whose frequencies deviate Significantly from the two
basic components, are small. In this case, the effect
of these components on the overall time evolution of the
wave packet is small. Examination of numerical re-
sults for the spectral decomposition of coherent Gauss-
ian wave packets in the HH potential 34 reveals that, for
wave packets located not too far from the fixed points,
either two frequencies dominate or the frequencies are
centered around two values in the spectra of these wave
packets. Thus, the classical analogy of overlap reduc-
tion is applicable for such wave packets.
Following the lifestory of the quantum-mechanical
(VI. 4) wave packet, we realize that at time scales exceeding
TD the wave packet will spread. The spreading of the
wave packet is expected to modify the analysis of the
preceding section in two ways. First, the time-depen-
dent second moments X/J(t) of the wave packet will ap-
pear in the Ehrenfest equations for (qJ) and (PJ)' While
the equations of motion for an initially coherent state in
the HH model start as the classical equations, wave
packet spreading phenomena result in the time depen-
dence of the Xi/t) and, consequently, the quantum-
mechanical equations of motion are modified at longer
times. The explicit modification of the quantum equa-
tions of motion depends, of course, on the details of the
spreading. In any case, at longer times, the quantum
wave packet dynamics expressed in terms of (PJ) and
(qJ) does not follow the classical trajectory dynamiCS.
,
Second, the effects of spreading are crucial for the de-
(VI. 5) tailed evolution of pet). When spreading effects are
Significant, the correspondence between P coCO and pet)
ceases to be valid, and the evolution of pet) has to be
conducted by quantum-mechanical methods. The
amount of spreading depends on the details of the en-
ergy spectrum, on the eigenstate composition of the
wave packet and on the initial conditions.
(VI. 6)
It is possible to gain considerable insight and obtain
some Significant qualitative results regarding quantum-
mechanical spreading effects by exploring the semi-
classical solutions for the energy levels 33 of the HH
(VI.6a) system. The semiclassical theory for integrable sys-
tems provides quantization conditions in terms of in-
variant tori. In the HH potential, one encounters stable
systems of relatively compact invariant tori surrounding
the elliptic periodic orbits, which persist up to the dis-
sociation energy. 12 Applying the semiclassical quan-
tization conditions for such a system of tori would re-
sult in a relatively regular spectrum and in wave func-
tions localized around the periodic orbits. This is in-
deed the case, as demonstrated by the results of the de-
tailed calculations reported by Weissman and Jortner. 33
The energy levels E(N,L) of the HH system, where N
is the multiplet index, and L =N, N - 2, ••• , -N the
"angular momentum," could be well represented by the
formula 33
E(N, L)/lrw =N + 1+ «(2/12)(_ 5N 2 -ION + 7L2 - 5) + 0«(4) •
(VI. 7)
 4182 M. Bixon and J. Jortner: Quantum dynamics of the Henon-Heiles system
We shall start the discussion of quantum-mechanical
spreading by considering the quantum-mechanical be-
havior of P(t), initiated at the fixed points of the
Poincare sections. For these classical periodic or-
bits, P co(t) is perfectly periodic, which implies that the
energy spectrum of the quantum wave packet is highly
regular. Small deviations of this spectrum from regu-
larity will result in spreading effects, which we shall
now consider. The classical periodic orbits TI7 and
TIs (Figs. 1 and 2) describe rotational motion, and, as
the potential itself is not sperically symmetric, the TI7
and TIa periodic orbits are characterized by large values
of quasiangular momentum. The analogous quantum
states are those characterized by large values of the
angular momentum quantum number L. Taking the
highest possible L for each multiplet N, i. e., L =±N,
results in the highly regular spectrum
E(N, ± N)/liw =N + 1 + (E: 2/12)(2N 2 - ION - 5),
and in the energy differences between consecutive ener-
gy levels
E[(N + 1),± (N'f 1)] - E(N, ±N) = 1- i E: 2 + ~ NE:2
liw .
so that when E: « 1 the relative deviation oEN of the dif-
ferences between consecutive levels, from the com-
pletely regular spectrum, is oE. =~ IN -(N)I E: 2 « 1,
where (N) is an average value of N for the states con-
stituting the wave packet. A similar situation prevails
for the classical periodic trajectories TIl, TI z, and TI 3.
In this case, the quasiangular momentum should be
small. Taking L = 0, one obtains the energy differences
between consecutive energy levels:
E(N+1,0)-E(N,0)_1 L2 LNz
liw - -4 E: -6 E:
Once again, the relative deviation from a regular spec-
trum is small, being oEN =~I N -(N)I E: 2 « 1, although it
is somewhat larger than in the previous case. We shall
now introduce a spreading time Ts for the quantum wave
packet, which in general depends on the initial condi-
tions. For coherent states located initially on classi-
cal periodic orbits, T. is defined by the reciprocal val-
ue of the mean value of the relative deviation, averaged
over the states constituting the wave packet:
where (oEN ) is a mean value of oEN averaged over all
the relevant states.
The detailed calculations of the energy spectrum and
the time evolution of initially coherent wave packets,
performed by Weissman and Jortner, 34 demonstrate
that coherent states located on the classical periodic
trajectories TI7 and TIa are composed almost exclusively
from the states with the highest quasiangular momen-
tum, i. e., L =± N. The spreading time for these wave
packets is, according to Eq. (VI.10),
Ts = [t (oN) E:Z]-l w- l , (VI. 11)
where (ON) is the spread in N values for states contri-
buting to the wave packet. We note that WTs» 1, so
that Ts is long. For the coupling strength E: = 0.085,
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employed in the numerical calculations,33 taking (oN)
"" (N) /2 = 5, one gets WTs = 100. Accordingly, for co-
herent states initially centered on the TI7 and TIa trajec-
tories, the classical description of the features of P(t),
advanced in the preceding section, would be correct for
many periods.
A similar situation prevails for coherent wave packets
located initially on the periodic traj ectories TI h TI z, and
TI 3' These wave packets are composed mainly, but not
exclusively, from states with low values of the angular
momentum, 1. e., L = 0 (and L = 1). The spreading time
in this case is
(VI. 12)
being somewhat shorter than that for the TI7 and TIs or-
bits.
Next, we consider some features of spreading of
(VI. 8)
wave packets located initially on quasiperiodic classi-
cal trajectories. The invariant tori located far from the
elliptic periodiC orbits are much larger in their spatial
extent. Accordingly, the quantum states related to them
(VI. 8a) are spread over large portions of the configuration
space. Therefore, coherent states that are initiated
far from the periodic trajectories involve a large num-
ber of different eigenstates with an irregular energy
spectrum. Consequently, the spreading time becomes
shorter when the initial pOSition of the wave packet
moves farther away from the periodic trajectory. The
shortening of the quantum-mechanical spreading time
can be traced to the contribution of a large number of
unevenly spaced eigenstates to the energy spectrum of
the wave packet. It should be noted, however, that this
irregularity in the spectrum does not necessarily re-
flect the quantum analog of claSSical chaotic behavior.
• (VI. 9)
Wave packets initiated far away from a classical pe-
riodic trajectory will be characterized by a short
spreading lifetime. The lower limit for the spreading
time corresponds to the dephasing time TD , Eq. (VI. 4).
The upper limit for the spreading time characterizes
wave packets initiated on periodic trajectories. One
can then set upper and lower limits for the spreading
time of any coherent wave packet
(VI. 13)
(VI. 10) These general considerations provide us with signifi-
cant qualitative information concerning the quantum-
mechanical initial-state population probability p(t),
which are borne out by detailed numerical calculations.
The features of P{t) are:
(1) For wave packets located initially on TI7 and TIe,
P(t) is periodic for long times. The periodic behavior
originates solely from classical effects (Sec. V). At
long times, quantum-mechanical spreading will set in,
eroding the periodic behavior. The spreading time,
Eq. (VI. 10) is long, being T. "" 100/ W for E: = 0.085 and
(N) =10.
(2) For wave packets initiated on TIl' TI 2 , and TI 3,
P(t) is periodic for quite long times, this purely classi-
cal periodic behavior being subsequently eroded by
spreading. The spreading time, Eq. (VI. 10), is T.
J. Chern. Phys., Vol. 77, No.8, 15 October 1982
 M. Bixon and J. Jortner: Quantum dynamics of the Henon-Heiles system
=301 w for E: =O. 085 and (N) =10.
(3) As the center of the wave packet is moved away
from the periodic trajectory, P(t) will exhibit a decay
originating essentially from classical overlap reduction
effects, which were discussed in Sec. V. The classical
behavior, which implies the resurrection of the overlap
at t"" TR (Sec. V) will be eroded by spreading effects,
as one expects that T s < T R'
(4) Wave packets initiated far away from the periodic
traj ectories, but still in the integrable region (for which
CNR » 1), are expected to exhibit rapid initial decay,
with only the first peak in P(t) being exhibited. This
initial behavior is due essentially to classical effects.
The spreading time in this case is short, being close
to T D , which will result in the erosion of all classical
features of P(t) at longer times. In particular, as
T R » T s ' one expects no exhibition of any classical ap-
proximate recurrence effects in P(t). After the first
peak, P(t) will just exhibit a low amplitude "noisy"
time dependence.
(5) Wave packets initiated in the stochastic region
will exhibit just the first peak in P(t), which then de-
cays rapidly. This is implied, essentially, by the
classical features of stochastic trajectories. There is
no distinction, with regard to the properties of P(t),
between the quantum dynamics of wave packets initiated
in the stochastic nonintegrable region and those initiated
far away from period trajectories in the integrable re-
gions. In both cases, P(t) exhibits the first peak, which
decays on the time scale of T D , Eq. (VI. 4), and subse-
quently P(t) reveals a low-amplitude noisy time depen-
dence.
We conclude the present discussion of quantum spread-
ing effects with two general observations. First, for
times that are short relative to the spreading times
t < T s' P(t) faithfully reflects the classical behavior of
trajectory dynamics. Second, for long times compared
to the spreading time t> T., P(t) exhibits an erratic
noisy time dependence with small amplitudes, whose
properties are similar for all initial positions of the
wave packet. This universal behavior may be described
as low-amplitude noisy time evolution. The nature of
the specific initial state will be reflected in the average
amplitude and fluctuations of the noisy time dependence.
VII. LONG-TIME FEATURES OF QUANTUM
DYNAMICS
The quantum-mechanical spreading time marks the
upper limit of the time domain, beyond which the classi-
cal notions based on trajectory dynamics are no longer
applicable to describe quantum dynamics. For long
times t» T., the only significant information concern-
ing quantum dynamics will originate from the explicit
form of P(t).
To analyze the long-time dependence of P(t), Eq.
(VI. 3), we separate it into interference terms and time-
independent terms
(VII. 1)
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4183
We consider the long-time behavior of the wave packet
when the correlation between the components of the
wave packet disappears. For the sake of a rough esti-
mate of the contribution of the noisy background to P(t)
at long times, we may assert that the coarse graining
contribution of the first term in Eq. (VI. 4) does vanish,
whereupon at t> Ts one has the average coarse grained
value P(t) "" 2:" I An 14. When no discrete eigenstates sig-
nificantly contribute to the wave packet, one expects,
on the basis of the normalization condition (VI. 2), that
an average value of the preparation amplitude is (IAnl ~
=1/no, so that p(t)-l/no at t> Ts' A wave packet
started initially at a classical periodic elliptic trajec-
tory contains an appreciable contribution from a single
state for each multiplet index N, so that no- 2(ON)- (N)
where (N) is the average multiplet index for those states con-
tributing to the wave packet, and we expect that p(t)-l/
(N). A wave packet located initially far away from a
classical periodic orbit spans a large number of (N, L)
eigenstates, all of which significantly contribute to it,
so that in this case no- 2(N) (ON) and p(t)-1I(N)2. These
rough estimates indicate that as (N) is large «N) -10-15
for E: =O. 085), we expect that both for wave packets ini-
tiated near periodic orbits and for those initiated far
away from them, p(t) is quite small, its average value
being, of course, appreciably higher in the former
case. One cannot specify further the general charac-
teristics of the noisy low amplitude behavior without
alluding to detailed numerical calculations.
The long-time features of P(t), when t» T., bear on
a central issue, pertaining to the possible manifestation
of classical stochasticity phenomena in quantum dynam-
ics. We recall that the time evolution of a wave packet
spans at all times only those eigenstates for which the
preparation amplitudes were initially finite, and that
the populations of these states are independent of time.
As t» T., the correlation between the components of
the wave packet disappears and the wave packet can be
viewed as a random superpOSition of its initial eigen-
states. A wave packet initiated on a periodic elliptic
trajectory has appreciable preparation amplitude only
for high-angular momentum states or for low-angular
momentum eigenstates, which are characterized by
large amplitudes only around this periodic trajectory.
Accordingly, at long times, such a wave packet will be
chaotically distributed around the periodic orbit. On
the other hand, wave packets which were initiated far
away from the periodic orbits will involve a superposi-
tion of a multitude of (N, L) states. Thus, for long
times such a wave packet will span large regions of the
configuration space. These long time features of the
wave packet initiated far away from a periodic trajec-
tory may be considered as reflecting "stochastic be-
havior." However, this quantum stochastic behavior
is not directly related to the classical stochastic prop-
erties. It just reflects the property of a wave packet
whose spectral resolution is not regular.
The last problem we would like to mention pertains
to the behavior of P(t), [Eq. (VI. 3)], at exceedingly
long times. It is well known that P(t) is a quasiperiodic
function of t with a large finite number of frequencies.
The quasiperiodic property originates from the baSic
 4184 M. Bixon and J. Jortner: Quantum dynamics of the Henon-Heiles system
property that only a finite number of eigenstates con-
tribute to the wave packet at all times. Therefore,
after exceedingly long time, we anticipate the reap-
pearance of the large initial amplitude (- 1) of P(t).
The quantum-mechanical recurrence time 7"~ is of the
order of the reciprocal common energy divider y, for
all the energy differences I En' - En I for the energies of
the states contributing to a wave packet:
(VII. 2)
Obviously, this quantum recurrence time is exceedingly
long for any system, such as the HH model. This ex-
ceedingly long quantum recurrence will be exhibited for
all wave packets of bound states, irrespective of the
initial conditions, so that, again, there is no qualitative
difference between wave packets initiated in classical
quasiperiodic and chaotic regimes. The quantum recur-
rence time is only of methodological interest, as in
real life additional damping effects, e. g., originating
from radiative decay, intermolecular collisions or wall
collisions, will erode all features of intramolecular dy-
namics at exceedingly long times.
VIII. CONCLUDING REMARKS
We are able to provide partial answers to the intri-
guing questions raised in the introductory section of
this paper, which pertain to the understanding of the
manifestations of the diverse features of quantum dy-
namics of wave packets in the Henon-Heiles (HH) sys-
tem. In what follows, we shall address these problems,
following the same order of presentation as in Sec. L
A. Correspondence between quantum wave packet
dynamics and classical dynamics
We have established a complete correspondence be-
tween quantum phenomena of wave packet dynamics and
classical trajectory dynamics on the time scale that is
shorter than the spreading time 7".. Limiting the dis-
cussion to this time scale, we can essentially identify
the classical trajectory overlap P co(t) with the exact
quantum-mechanical expression for P(t). On a longer
time scale t ~ 7"., wave packet spreading effect renders
P co(t) meaningless and we have to refer to P(t) for the
description of quantum dynamics. In a further pursuit
of classical-quantum analogies, we would like to point
out that although we have considered wave packet
spreading as a quantum-mechanical phenomenon, whose
gross features were elucidated in Secs. VI and VII on
the basis of quantum-mechanical formalism, classical
results can be utilized to obtain information concerning
the spreading time. The level structure, which was
based on a semiclassical approximation, was utilized in
Sec. VI to obtain information concerning 7"., whereupon
classical information based on the tori structure of the
phase space was exploited to obtain general estimates
of spreading times.
It is interesting to point out that a classical analog of
P(t) can be constructed, which exhibits the qualitative
features of its quantum-mechanical counterpart. Of
course, there is no classical analog of the quantum-
mechanical probability amplitude, whereupon one has
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to investigate the classical dynamics of a region in the
phase space. Let S(O) be a small sphere in the four-
dimensional phase space (it is not restricted to an en-
ergy surface). The classical time development of this
region consists of (a) motion and (b) deformation, so
that at time t it will occupy the region S(t) of the phase
space. We shall now define the classical time depen-
dent overlap P cl (t) between the region S(t) and the ini-
tial region
(VIII. 1)
where Jl.(.) stands for the measure (volume). The classi-
cal expression Pcl(t) , Eq. (VIII. 1) provides the classical
analog for the quantum-mechanical P(t), Eq. (IlL 1).
The rate of the deformation of the initial sphere de-
pends on its initial position. The deformation rate is
expected to be small when the sphere is initially located
in the vicinity of a periodic orbit, i. e., near a fixed
point on the Poincare section (Appendix A). The defor-
mation rate is expected to increase when the sphere is
initially moved away from a fixed point, and it will be-
come very large for a sphere initially located in the
stochastic region. Within the classical integrable re-
gion, the rate of the deformation of the disc on the
Poincare section can be estimated to be wC I \1NR I,
where w is the characteristic frequency, while I \1NR I
is the absolute value of the gradient of the rotation num-
ber NR (defined in Appendix A), and C is the circumfer-
ence of the closed line on the Poincare section. Near
the fixed point, C is small, and classical deformation
effects are negligible. In integrable regions far away
from fixed points, C is large, and rapid deformation
is exhibited. In the stochastic region, the separation
between initially, closed points grows exponentially
with time. Consequently, a small sphere in the phase
space would deform drastically and spread over large
regions of the classical chaotic domain. The same
phenomena of fast spreading of a region of the phase
space (on the energy shell) in a many-body system was
considered already a long time ago as an essential basis
for classical statistical mechanics. 4o The interesting
features of P cl (t) may be summarized as follows: (1)
For a sphere located initially on a periodic trajectory,
or close to it, the deformation rate is small and P cl (t)
is periodic, or slowly decay ing periodic function of
time. (2) When one moves away from the fixed point,
starting with a sphere (disc) centered on a closed curve
on the Poincare section, orbital overlap effects will re-
sult in a decay of P cl (t). (3) Moving further away from
a fixed point, the deformation rate increases, combin-
ing with classical overlap effects to enhance the decay
of P cl (t). (4) In the stochastic region, P cl (t) will exhibit
only the initial peak and a low-amplitude noisy back-
ground. These qualitative features of Pcl(t) are identical
to the characteristics of p(t). Still, one has to bear in
mind the basic differences between the two functions
P(t) and Pcl(t). p(t) measures the overlap between two
wave functions, while Pcl(t) measures the overlap be·
tween regions in phase space. It is not clear, at pres-
ent, what are the basic physical relations between these
two quantities. Although it would be very interesting to
explore the relation between Pcl(t) and P(t), we have
 M. Bixon and J. Jortner: Quantum dynamics of the Henon-Heiles system
resorted to a less ambitious attitude of exploring the
analogy between quantum dynamics of wave packets and
classical trajectory dynamics, investigating the rela-
tion between pco(t) and pet).
The implications of the complete correspondence be-
tween classical trajectory dynamics, expressed in
terms of P co(t) and quantum dynamics of pet) on the
time scale t < T., are as follows: (i) The (quasi) peri-
odic time evolution of pet) reflects the classical prop-
erties of a periodic traj ectory. (ii) The decay of p(t)
on the time scale of a few vibrational periods is essen-
tially analogous to the classical behavior of a quasipe-
riodic traj ectory. (iii) The decay of the intial state
population probability of wave packets initiated in the
integrable region involves a major contribution from
classical overlap reduction effects. (iv) The decay of
pet) is enhanced when the center of the wave packet
moves away from the fixed points on the Poincare sec-
tions until the ("short time") behavior of pet) is char-
acterized by a single initial pe~ fOllowed by a noisy
background. (v) The latter time evolution is qualita-
tively identical to that exhibited by wave packets initiated
in the classically chaotic region. There is no distinc-
tion between the short time behavior of pet) initiated in
distant, regular, integrable regions, and those initiated
in classically chaotic regions. ClaSSical chaotic behav-
ior cannot be inferred from short time quantum dynam-
ics as reflected in pet).
B. Quantum analog of the stochastic transition
As the short time behavior of P(t) cannot provide suf-
ficient conditions for the characterization of the quantum
analog of the classical chaotic behavior, we have to re-
fer to the long time features of pet) in this context. We
propose that quantum stochastic properties are re-
flected in the low-amplitude random noise behavior of
pet) at long times, which are a general universal prop-
erty of all quantum wave packets, irrespective of the
initial conditions. These universal long-time features
originate from the irregularity of the spectrum of the
wave packet, which is a general property of nonlinear
systems. Obviously, there are quantitative differences
in the quantum stochastic behavior of wave packets ini-
tially located at different positions. The noisy charac-
teristics of pet) with high amplitudes appear after a
long time for wave packets initiated close to periodic
orbits while, for wave packets starting far away from
the periodic orbits in the classical stochastic regime,
the noisy appearance of pet) is prompt and its amplitude
is low. We conclude with two general comments per-
taining to this cardinal problem. First, quantum sto-
chastic behavior in a bound level structure just reflects
the features of a wave packet whose spectral decomposi-
tion is irregular. Irregularity in the spectral decom-
pOSition is exhibited for all wave packets in a nonlinear
system. Only the degree of irregularity depends on the
initial conditions. Accordingly, quantum stochasticity,
as envisioned by us, is not directly related to classical
stochastic properties. Second, we were unable to es-
tablish, on the basis of wave packet dynamics, a quan-
tum-mechanical analog for the "critical" energy for the
"transition" from quasiperiodic to chaotic motion ex-
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4185
hibited in classical systems. The change in the char-
acter of the wave packet dynamics with changing of the
initial conditions is gradual.
C. Intrinsic quantum-mechanical effects
For nonharmonic systems, wave packets spreading
phenomena are exhibited, affecting the qualitative fea-
tures of the quantum dynamics. We were able to advance
a classical analog for the quantum wave packet spread-
ing phenomena in terms of deformation of a phase space
region. However, the quantum phenomenon of spreading
incorporates interference of probability amplitude, which
has no classical analog. Accordingly, the spreading
time T. has to be evaluated on the basiS of the quantum-
mechanical arguments. In this context, one has to dis-
tinguish carefully between general classical-quantum
analogies, i. e., pet) and P c1 (t), which exhibit qualita-
tively similar features over a large time scale, and the
correspondence between quantum dynamics and classi-
cal trajectory dynamics. In this context, we note that
the quantum-mechanical spreading time T s ' which it-
self is determined by the initial conditions, provides
the upper limit for the time scale, for which the classi-
cal concepts of orbit overlap, stemming from trajectory
dynamics, are still applicable for the description of
the quantum dynamics of the particular wave packet.
Quantum-mechanical spreading is exhibited only for
nonharmonic potentials, while for harmonic potentials
the coherent wave packet does not spread and the quan-
tum-classical analogies are valid for all times. For
nonharmonic systems on the time scale t> T s' all initial
phase relations are eroded, whereupon pet) exhibits a
universal, low-amplitude, noisy time evolution.
D. Decay of P ( t ) and wave packet spreading in separable
systems
The observation of the decay of P(t), which has a
clear analogy in terms of classical overlap reduction
effects, in the simple system of a two-dimensional har-
monic oscillator (Sec. IV), clearly demonstrates that
the initial decay of P(t) is not related to the nonsepara-
bility of the potential. Quantum interference effects
exhibited in nonharmonic systems are unrelated to
separability or to nonintegrability. This can easily be
demonstrated by considering the dynamics of a wave
packet, consisting of bound states of a one-dimensional
Morse oscillator, where the spreading time is To
-l/2Xw(v). Here, w is the frequency, X the anhar-
monicity, and (v) is the average vibrational quantum
number of states constituting the wave packet.
E. Hierarchy of time scales for dynamics
The relevant time scales, which can be traced to clas-
sical trajectory dynamics and to quantum phenomena,
are the Vibrational intermode period 211"w-t, the quantum-
mechanical dephasing time TD =nr- 1 (which has a clas-
sical analog), the classical overlap reduction time TO."
the quantum-mechanical spreading time Ta , the classi-
cal approximate recurrence time TR for quasiperiodic
motion, and the quantum-mechanical recurrence time
T~ for all wave packets. The distinction between quasi-
 4186 M. Bixon and J. Jortner: Quantum dynamics of the Henon-Heiles system
periodic and chaotic dynamics is reflected in the classi-
cal time scales, which pertain to overlap reduction and
to approximate recurrence effects. However, also in
the integrable region, Tov can be exceedingly short
(- T D ), and no sharp distinction between integrable and
nonintegrable regions can be established, while classi-
cal approximate recurrence effects are expected to be
eroded by quantum-mechanical spreading. Recurrence
phenomena exhibited on the exceedingly long time scale
T~, for the quantum dynamics of the wave packet, are
of no methodological interest, as they reflect quasipe-
riodicity of P(t) and are expected to be exhibited, both
for wave packets initiated in regular and in chaotic re-
gions. From the practical point of view, these quan-
tum recurrence phenomena are irrelevant, as they will
be dumped by radiative and by collisionally induced de-
cay processes.
ACKNOWLEDGMENTS
We are indebted toDr. Y. Weissman and to Professor
J. Brickmann for many illuminating discussions. This
research was supported in part by the United States-
Israel Binational Science Foundation (Grant No. 2641),
Jerusalem, Israel.
APPENDIX A: SOME RESULTS OF CLASSICAL
MECHANICS OF THE HENON-HEILES SYSTEM
We shall now review some of the results emerging
from classical mechanics of the Henon-Heiles (HH)
system, 4,12 which will be relevant for the comparison
between the quantum wave packet dynamics and the
classical trajectory dynamics
1. Periodic orbits
At each energy, there exist eight simple periodic or-
bits designed as TIl'" TIs (Fig. 1). TIl' TI 2 , TI 3, TI 7 , and
TIs are stable elliptical orbits, while TI 4 , TIs, and TIs are
hyperbolic orbits.
2. Quasiperiodic and chaotic trajectories
Other trajectories are either quasiperiodic or chaotic,
depending on the region in phase space. At low ener-
gies, all the trajectories are quasiperiodic. As the
energy is increased, the chaotic trajectories span larger
regions. The region of chaotic trajectories develop
space when the energy is close to the dissociation en-
ergy. QuaSiperiodic traj ectories exist at all energies
around the elliptic periodic orbits.
To use the language of modern theoretical mechanics,
the three-dimensional constant energy surface of the
four-dimensional phase space is composed, at low en-
ergies, entirely of invariant two-dimensional tori. At
higher energies, some of the tori are destroyed, but the
elliptic periodic orbits are surrounded by such tori at
any energy.
3. Poincare sections
The classical dynamics of the HH system is usually
represented on the two-dimensional Poincare sections
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of the phase space. The most common representation
is the section q1 =0, expressed in terms of q2 and P2'
On this section, the periodic orbits, with the exception
of TIl, are represented by points, while TIl is the perim-
eter of the allowed region (Fig. 2). The sections of the
invariant tori, on which the quasiperiodic trajectories
are located, appear as closed curves. Each closed
curve is characterized by its rotational number N R ,
which is defined as the relative angular separation be-
tween two consecutive crossings of the section (angular
separation/21T). Systems of closed curves surround
the elliptic fixed point (periodic orbits). The rotational
numbers change continuously, starting from zero at the
fixed point and increasing gradually when one moves
away from a fixed point.
4. Topology of Poincare sections
At low energies, the Poincare section is completely
covered by closed curves, i. e., sections of invariant
tori. At higher energies, when invariant tori begin to
break down, the sections spanned by closed curves
begin to disappear, being replaced by two-dimensional
regions covered with points, which are the reiterates
of the same state. This behavior begins near the hy-
perbolic fixed points, i. e., the hyperbolic periodic or-
bits. The irregular regions grow with increasing en-
ergy. Around each elliptic fixed point, there remain
systems of closed curves, i. e., sections of invariant
tori. In principle, inside such systems there are very
thin regions of broken tori.
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