Quantized Hamilton dynamics

Cite as: J. Chem. Phys. 113, 6557 (2000); https://doi.org/10.1063/1.1290288

Submitted: 18 May 2000 • Accepted: 11 July 2000 • Published Online: 12 October 2000

Oleg V. Prezhdo and Yu. V. Pereverzev

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J. Chem. Phys. 113, 6557 (2000); https://doi.org/10.1063/1.1290288 113, 6557

© 2000 American Institute of Physics.

JOURNAL OF CHEMICAL PHYSICS VOLUME 113, NUMBER 16 22 OCTOBER 2000

Quantized Hamilton dynamics

Oleg V. Prezhdo and Yu. V. Pereverzev
Department of Chemistry, University of Washington, Seattle, Washington 98195-1700
共Received 18 May 2000; accepted 11 July 2000兲
The Hamilton approach to classical dynamics is extended to incorporate quantum effects.
Quantization of the Hamilton equations of motion results in a hierarchy of equations that are
equivalent to quantum mechanics in the Heisenberg form. Closure of the hierarchy gives
approximations to the exact quantum dynamics. A specific dynamics algorithm is presented and
tested against model applications that exhibit tunneling and zero point motion effects. The quantized
Hamilton approach is found accurate, consistent, flexible, and computationally very efficient.
© 2000 American Institute of Physics. 关S0021-9606共00兲00638-3兴

I. INTRODUCTION Another type of the quantum-classical approximation is

Nonrelativistic quantum mechanics provides a rigorous
framework for investigation of most problems encountered
in chemistry. Nevertheless, more often than not it is much
easier to treat problems classically, rather than quantum me-
chanically. Each quantum mechanical degree of freedom re-
quires an infinitely dimensional Hilbert space. Classically,
the Hilbert space is mapped onto a two-dimensional phase
space. Low dimensionality and computational simplicity of
classical mechanics provides a strong driving force for clas-
sical and mixed quantum-classical approaches. A separation
of a system into quantum and classical parts can be based on
relative masses or energies associated with different degrees
of freedom. For example, molecules consisting of electrons
and nuclei are customarily split into quantum and classical
subsystems and are viewed as a collection of quantum-
mechanical electrons moving in the field of classical nuclei.
This description gives the Born–Oppenheimer approxima-
tion that is justified by the large ratio of the nuclear and
electronic masses. High frequency vibrational modes of the
nuclei can be also treated quantum mechanically, while the
low frequency modes are described classically. The high/low
frequency separation of the vibrational modes is justified by
the number of available quantum states that depends on the
total energy relative to the quantum of vibrational energy. In
both cases, quantum and classical mechanics are applied to
different degree of freedom. The quantum and classical de-
grees of freedom are then coupled to each other. The cou-
pling scheme is not unique. Various quantum-classical meth-
ods that differ in the coupling procedure have been
developed.1–30 Classical p and q can be coupled to the cor-
responding quantum expectation values based on the Ehren-
fest theorem.31 The result is the mean-field
approach.2–4,12,13,20,24,26 Extensions of the mean-field method
to include higher order quantum observables lead to multi-
configuration mean-field1,16,26,28 and surface
2,3,6–13,25,27
hopping methods, where several classical trajecto-
ries are coupled to a single quantum mechanical evolution.
Application of these methods range from gas phase scatter-
ing reactions9,14,15,22,32–34 to surface,11,35 solution,7,8,10,36–38
and biological chemistry.39,40
needed when the same degree of freedom is neither classical,
nor fully quantum-mechanical. For example, the same mode
can switch between quantum and classical regimes depend-
ing on the available energy. Situations of this sort are, per-
haps, more common than the purely classical/purely quan-
tum combinations. Proton motion from one water molecule
to the next involves quantum tunneling. At the same time, a
proton attached to the one molecule is well described by
classical mechanics. A wide amplitude torsional motion
around a C–C bond in a molecule such as ethane CH3 –CH3
is very well described classically, except near the top of the
rotation barrier where tunneling through the H•••H repulsion
becomes important. The borderline between quantum and
classical behaviors of the same particle depends on particle’s
energy. The CH3 –CH3 torsional motion is classical at high
energies. When the total energy is close to the energy of the
rotational barrier, tunneling comes into play. As the energy is
lowered further, the dynamics once again becomes classical.
At very low energies, the torsional motion proceeds around
the minimum of the potential, and the quantum zero point
energy 共ZPE兲 effect dominates. In a diatomic molecule, ZPE
plays its role at low vibrational energy, but is negligible near
the dissociation limit. Examples of this kind can be found in
all states of matter and systems of any size.
Several approaches that deal with tunneling, ZPE
and other quantum corrections to classical mechanics
have been proposed. Various semiclassical
methods5,14–17,20–22,41–46 link quantum and classical mechan-
ics. Tunneling is typically treated via WKB approximations,
where the tunneling amplitude is calculated along a trajec-
tory that connects the point of entrance into the barrier with
the exit point.41,42,45,46 Straightforward in one dimension,
semiclassical description of tunneling becomes more compli-
cated in many dimensions.45,46 While the entrance into the
barrier is specified by the point where the classical trajectory
hits the barrier, the exit point is not unique. All possible exit
points should be sampled and imaginary time trajectories
should be propagated that connect the entry and exit
points.14,15,42 The multiple spawning approach to tunneling47
is a variant of this procedure, where the tunneling probability
is determined by the overlap of Gaussian wavepackets rep-

0021-9606/2000/113(16)/6557/9/$17.00 6557 © 2000 American Institute of Physics

6558 J. Chem. Phys., Vol. 113, No. 16, 22 October 2000
resenting classical particles, rather than from the WKB ap-
proximation. In order to account for ZPE using classical me-
chanics, classical trajectories are sorted out by certain criteria
that are designed to exclude trajectories without ZPE.43,44,48
The difficulty of such approaches lies in the fundamental fact
that ‘‘criteria based on the behavior of individual trajectories,
independent of the behavior of the ensemble, are not
valid.’’44 Simulation of ensembles of coupled trajectories can
be very expensive computationally in many-dimensional sys-
tems. The coupling terms are typically very sensitive to the
density of trajectories. Trajectories rapidly diverge, and sta-
tistical ensembles of very large sizes are required for good
convergence. The nonlocal nature of quantum mechanics
complicates development of semiclassical methods based on
swarms of trajectories, as observed in a number of approxi-
mate schemes.49–55
The approach introduced in the present paper extends
classical Hamilton mechanics in a conceptually novel way. It
provides a unified scheme for treatment of ZPE, tunneling
and other quantum effects. The method is motivated by the
ideas of mixed quantum-classical dynamics. In contrast to
the existing quantum-classical schemes that couple purely
classical and purely quantum mechanical degrees of free-
dom, the new approach considers coupling of quantum and
classical mechanics for the same degree of freedom. The
method gives Hamilton equations of motion 共EOM兲 for p
and q that are coupled to EOMs for other dynamical vari-
ables arising from quantum mechanics. The Hamilton dy-
namics is quantized by coupling to the quantum variables.
Hence, the method is called quantized Hamilton dynamics
共QHD兲. The theory section presents our motivation for QHD
and develops a QHD algorithm. The method is then applied
to one and two-dimensional models of tunneling and ZPE
effects. The concluding section summarizes the features of
the method and discusses further avenues for consideration
and improvement.
II. THEORY
Consider a time-dependent problem that can be solved
exactly in classical mechanics, either analytically or numeri-
cally, but can not be solved in quantum mechanics. Suppose
that an approximation to the full problem exist that admits a
quantum mechanical solution. For instance, ZPE in a highly
anharmonic dissociation of a diatomic is well described in
the harmonic approximation. Tunneling of proton from one
water molecule to the next is well described by the instanton
model56,57 that is based on the inverted harmonic potential.
The following question arises in both cases: Is it possible to
combine the exact classical and approximate quantum solu-
tions?
A. Quantum-classical mixing for separate degrees of
freedom
In situations where some degrees of freedom (p,q) ad-
mit the classical limit and the remaining degrees ( P,Q) can
be treated quantum mechanically, the quantum-classical mix-
ing is given by the quantum-classical Lie bracket1,29,30
O. V. Prezhdo and Y. V. Pereverzev
i
关关 A,B 兴兴 ⫽ 关 A,B 兴 ⫹ 兵 A,B 其 . 共1兲
ប
The bracket is the sum of the quantum commutator 关쐓, 쐓兴
and the classical Poisson bracket 兵쐓, 쐓其. Separation of the
total system into quantum and classical subsystems defines a
state space that is a direct sum of the quantum Hilbert and
classical phase spaces. Observables, including the Hamil-
tonian, are functions of quantum operators acting in the Hil-
bert space and classical p and q in the phase space. For
example, if an observable is a product of quantum ␣, ␤ and
classical a, b functions, such as in a quantum-classical cou-
pling term Qq, the corresponding Lie bracket has the form
关关 ␣ 共 P̂,Q̂ 兲 a 共 p,q 兲 , ␤ 共 P̂,Q̂ 兲 b 共 p,q 兲兴兴
i
⫽ 关 ␣ , ␤ 兴 ab⫹ 兵 a,b 其 共 ␣␤ ⫹ ␤␣ 兲 /2. 共2兲
ប
The evolution of an observable A is given by its quantum-
classical bracket with the Hamiltonian H
⳵A
⫽ 关关 A,H 兴兴 . 共3兲
⳵t
Detailed and rigorous definitions of expressions 共1兲–共3兲 fol-
low from the mixed quantum-classical representation of the
product of two Heisenberg groups as discussed in Ref. 1.
B. Quantum-classical mixing for the same degree of
freedom
We would like to use this approach in order to combine
the exact classical and approximate quantum solutions for
the same particle. We focus on the EOM first. Since a low
order potential can provide a good approximation for the
ZPE and tunneling effects, we Taylor expand the potential
energy. The quantum Hamiltonian H 0 will include only the
lower order terms in the expansion
H 共 P̂,Q̂ 兲 ⫽H 0 共 P̂,Q̂ 兲 ⫹V 共 Q̂ 兲 ,
共4兲
P̂ 2
H 0 共 P̂,Q̂ 兲 ⫽ ⫹V 0 共 Q̂ 兲 .
2m
The exact time evolution of the expectation value of a quan-
tum observable A( P̂,Q̂) is given in the Heisenberg represen-
tation by
⳵ 具 A 共 P̂,Q̂ 兲 典 i
⫽ 具 关 A 共 P̂,Q̂ 兲 ,H 0 共 P̂,Q̂ 兲 ⫹V 共 Q̂ 兲兴 典 , 共5兲
⳵t ប
where the angular brackets denote quantum mechanical av-
eraging, e.g., 具 A( P̂,Q̂) 典 ⬅ 具 ⌿ 兩 A( P̂,Q̂) 兩 ⌿ 典 . The wave func-
tion 兩 ⌿ 典 is time independent in the Heisenberg picture and is
determined by the initial conditions.
The quantum-classical approximation is achieved by ap-
proximation of the quantum commutator between A and the
higher order potential energy terms with the Poisson bracket.
The kinetic and low order potential energy terms are treated
in the usual quantum mechanical way. The proposed
quantum-classical EOM is
J. Chem. Phys., Vol. 113, No. 16, 22 October 2000
⳵ 具 A 共 P̂,Q̂ 典 兲 i
⫽ 具 关 A 共 P̂,Q̂ 兲 ,H 0 共 P̂,Q̂ 兲兴 典
⳵t ប
⫹ 兵 A 共 p,q 兲 ,V 共 q 兲 其
where p⬅ 具 ⌿ 兩 P̂ 兩 ⌿ 典 , q⬅ 具 ⌿ 兩 Q̂ 兩 ⌿ 典 .
It remains to be seen whether the right-hand side of Eq. 共6兲 is
a true Lie bracket that obeys the same properties as the clas-
sical Poisson bracket and quantum commutator. A group the-
oretical analysis similar to that of Ref. 1 for the quantum-
classical bracket 共1兲 may provide a rigorous definition of Eq.
共6兲. As suggested by Kisil58 this could be achieved by the G 2
Lie group with five elements 兵 P,Q,q,iប,iប̃ 其 satisfying the
following commutation relationships: 关 P,Q 兴 ⫽iប, 关 P,q 兴
⫽iប̃, all other commutators being equal zero.59 The limit
ប̃→0 could provide the desired quantum-classical represen-
tation if the total Hamiltonian 共4兲 is viewed as a function of
P, Q, and q: H( P̂,Q̂,q)⫽H 0 ( P̂,Q̂)⫹V(q). The issue de-
serves a separate analysis. We note that if the classical limit
as in Eq. 共6兲 is taken in Eq. 共5兲 for both H 0 and V, the
classical EOMs are obtained
dp ⳵ 共 V 0 共 q 兲 ⫹V 共 q 兲兲 dq
⫽⫺ , ⫽p.
dt ⳵q dt
We consider EOM 共6兲 for a set of the quantum mechani-
cal average values of momentum, position operators and
their products 具 P̂ 典 , 具 Q̂ 典 , 具 P̂ 2 典 , 具 Q̂ 2 典 , 具 P̂Q̂ 典 ,... . The EOMs for
the average values are coupled and, in general, form an infi-
nite hierarchy. The hierarchy is terminated by the approxi-
mation of the higher order averages via products of the lower
order averages. The closure scheme is presented below and
leads to the QHD algorithm.
C. The QHD algorithm
We work in the Heisenberg representation, where opera-
tors evolve in time, while the time-independent wave func-
tion 兩 ⌿ 典 specifies initial conditions.
Step 1. Variables. A set A of quantum mechanical ob-
servables that are functions of the position and momentum
operators is defined
A⬅ 兵 P̂, Q̂, P̂ 2 , Q̂ 2 , 共 P̂Q̂ 兲 s , . . . 其 .
The cross terms are Weyl symmetrized,1,60 e.g.,
P̂Q̂⫹Q̂ P̂
共 P̂Q̂ 兲 s ⬅ . ⬇ 具 AB 典具 C 典 ⫹ 具 AC 典具 B 典 ⫹ 具 BC 典具 A 典 ⫺2 具 A 典具 B 典具 C 典 ,
2
The dynamical variables of the QHD method are defined by
the quantum mechanical expectation values of the observ-
ables in the set taken with respect to the time-independent
wave function
具 A 典 ⬅ 兵 具 P̂ 典 , 具 Q̂ 典 , 具 P̂ 2 典 , 具 Q̂ 2 典 , 具 P̂Q̂ 典 s , . . . 其
with 具 P̂ 典 ⫽ 具 ⌿ 兩 P̂ 兩 ⌿ 典 , etc.
The set must contain the first order terms 具 P̂ 典 and 具 Q̂ 典 .
Quantized Hamilton dynamics 6559
Step 2. Quantum-classical Hamiltonian. The total
Hamiltonian is split into the quantum H 0 and classical V
parts as in Eq. 共4兲, for example, by Taylor expansion of the
potential energy.
P̂ 2
H 共 P̂,Q̂ 兲 ⫽ ⫹V 0 共 Q̂ 兲 ⫹V 共 具 Q̂ 典 兲 ,
2m
共6兲
共10兲
具 Q̂ 典 ⬅ 具 ⌿ 兩 Q̂ 兩 ⌿ 典 .
The kinetic and low order potential V 0 energy term remains
an operator valued function, while the higher order potential
energy term V is a number valued function of the average
quantum position.
Step 3. Equation of motion. Each dynamical variable
具 P̂ Q̂ 典 s from the set 共9兲 evolves according to the quantum-
m n
classical equation of motion 共6兲
⳵ 具 P̂ m Q̂ n 典 s i
⫽ 具 关共 P̂ m Q̂ n 兲 s ,H 0 共 P̂,Q̂ 兲兴 典
⳵t ប
⫹ 兵 具 P̂ 典 m 具 Q̂ 典 n ,V 共 具 Q̂ 典 兲 其 . 共11兲
The quantum mechanical average of the commutator pro-
duces a new dynamical variable which may or may not be-
long to the set 共9兲. If the new variable does not belong to the
set 共9兲, the closure procedure is applied.
共7兲 Step 4. Closure scheme. For nontrivial H 0 , the commu-
tator in Eq. 共11兲 increases the power of ( P̂ m Q̂ n ) s introducing
higher order dynamical variables 具 P̂ m Q̂ n 典 s . For example, a
cubic term in the potential energy couples the linear variable
具 P̂ 典 to the second order variable 具 Q̂ 2 典 . At some point, a
newly generated variable 具 P̂ m Q̂ n 典 s will be outside the set of
the selected dynamical variables, Eq. 共9兲. The extra variable
具 P̂ m Q̂ n 典 s is approximately decomposed into a product of the
lower order variables from the set 共9兲, terminating the EOM
hierarchy. The closure procedure is similar to that in
statistical61–63 and quantum64,65 many-body theory. The av-
erage 具 P̂ m Q̂ n 典 s is decomposed into the irreducible parts and
the highest (m⫹n)-order irreducible term is represented by
the sum of all possible products of the lower order irreduc-
ible terms. Decompositions for the third and fourth order
terms are given by all possible pairings of the individual
operators, as in Wick’s theorem.64 Thus, the following clo-
sure is obtained for a general third order term
具 ABC 典 ⫽ 具 共 A⫺ 具 A 典 ⫹ 具 A 典 兲共 B⫺ 具 B 典 ⫹ 具 B 典 兲共 C⫺ 具 C 典 ⫹ 具 C 典 兲 典
共8兲
⫽ 具 共 A⫺ 具 A 典 兲共 B⫺ 具 B 典 兲共 C⫺ 具 C 典 兲 典 ⫹ 具 AB 典具 C 典
⫹ 具 AC 典具 B 典 ⫹ 具 BC 典具 A 典 ⫺2 具 A 典具 B 典具 C 典
共12兲
since all the pairings
具 共 A⫺ 具 A 典 兲共 B⫺ 具 B 典 兲共 C⫺ 具 C 典 兲 典
⬇ 具 共 A⫺ 具 A 典 兲共 B⫺ 具 B 典 兲 典具 共 C⫺ 具 C 典 兲 典
⫹ 具 共 A⫺ 具 A 典 兲共 C⫺ 具 C 典 兲 典具 共 B⫺ 具 B 典 兲 典
共9兲 ⫹ 具 共 B⫺ 具 B 典 兲共 C⫺ 具 C 典 兲 典具 共 A⫺ 具 A 典 兲 典 ⫽0 共13兲
vanish. Fourth order terms are decomposed into
6560 J. Chem. Phys., Vol. 113, No. 16, 22 October 2000
具 ABCD 典 ⫽ 具 共 A⫺ 具 A 典 兲共 B⫺ 具 B 典 兲共 C⫺ 具 C 典 兲共 D⫺ 具 D 典 兲 典
⫹ 具 ABC 典具 D 典 ⫹ 具 ABD 典具 C 典 ⫹ 具 ACD 典具 B 典
⫹ 具 BCD 典具 A 典 ⫺ 具 AB 典具 C 典具 D 典 ⫺ 具 AC 典具 B 典具 D 典
⫺ 具 BC 典具 A 典具 D 典 ⫺ 具 AD 典具 B 典具 C 典 ⫺ 具 BD 典具 A 典具 C 典
⫺ 具 CD 典具 A 典具 B 典 ⫹3 具 A 典具 B 典具 C 典具 D 典 . 共14兲
The pairing procedure gives
具 共 A⫺ 具 A 典 兲共 B⫺ 具 B 典 兲共 C⫺ 具 C 典 兲共 D⫺ 具 D 典 兲 典
⬇ 具 共 A⫺ 具 A 典 兲共 B⫺ 具 B 典 兲 典具 共 C⫺ 具 C 典 兲共 D⫺ 具 D 典 兲 典
⫹ 具 共 A⫺ 具 A 典 兲共 C⫺ 具 C 典 兲 典具 共 B⫺ 具 B 典 兲共 D⫺ 具 D 典 兲 典
⫹ 具 共 A⫺ 具 A 典 兲共 D⫺ 具 D 典 兲 典具 共 B⫺ 具 B 典 兲共 C⫺ 具 C 典 兲 典 . 共15兲
The 3⫹1 decompositions such as 具 (A⫺ 具 A 典 )(B⫺ 具 B 典 )
⫻(C⫺ 具 C 典 ) 典具 (D⫺ 具 D 典 ) 典 vanish, and the final closure for-
mula for the fourth order term reads
具 ABCD 典 ⬇ 具 ABC 典具 D 典 ⫹ 具 ABD 典具 C 典 ⫹ 具 ACD 典具 B 典
⫹ 具 BCD 典具 A 典 ⫹ 具 AB 典具 CD 典 ⫹ 具 AC 典具 BD 典
⫹ 具 AD 典具 BC 典 ⫺2 具 AB 典具 C 典具 D 典 ⫺2 具 AC 典具 B 典具 D 典
⫺2 具 BC 典具 A 典具 D 典 ⫺2 具 AD 典具 B 典具 C 典
⫺2 具 BD 典具 A 典具 C 典 ⫺2 具 CD 典具 A 典具 B 典
⫹6 具 A 典具 B 典具 C 典具 D 典 . 共16兲
Higher order terms can be decomposed in a similar
manner.62
It is straightforward to show based on the Ehrenfest
theorem31 that when the set of variables 共8兲 is restricted to
contain only the momentum and position operators A
⫽ 兵 P̂,Q̂ 其 , the QHD algorithm gives the Hamilton EOMs of
classical mechanics for any quantum-classical Hamiltonian
共4兲. The Poisson bracket in the quantum-classical EOM 共6兲,
共11兲 is essential for the classical limit in the presence of the
high order terms V in the Hamiltonian 共4兲, 共10兲.
III. APPLICATIONS
The QHD method is applied in present to two model
systems that exhibit tunneling and ZPE phenomena. The
Hamiltonians in both models are anharmonic only to low
order, so that the quantum Hamiltonian H 0 is the full Hamil-
tonian H, Eqs. 共4兲 and 共10兲. The QHD calculations are com-
pared with the classical mechanics results as well as with the
fully quantum mechanical calculations. The classical and
QHD simulations are performed numerically using the fourth
order Runge–Kutta integrator. The classical and QHD calcu-
lations take about the same amount of time and are several
orders of magnitude faster than the quantum mechanical cal-
culation. The quantum mechanical wave packets are propa-
gated by the split-operator method66 using fast Fourier trans-
form to switch between position and momentum
representations. The calculation results are tested for conver-
gence with respect to the integration time step and, in the
quantum mechanical case, with respect to the grid size and
spacing. The initial conditions of quantum, classical and
O. V. Prezhdo and Y. V. Pereverzev
FIG. 1. Potential energy as a function of particle position 具 Q̂ 典 in the tun-
neling example, Eq. 共18兲. The barrier maximum is located at q⫽⫺3.33 and
has the height of 1.85.
QHD simulations correspond to the Gaussian wave packet
that has the following form in the position representation:
⌿共 q 兲⫽ 冉 冊 冋
m␻
␲ប
1/4
exp ⫺
m ␻ 共 q⫺q 0 兲 2
2ប
⫹i
p 0q
ប 册 for t⫽0,
共17兲
where q 0 is the center of the wave packet and p 0 is its initial
momentum. The units in both examples are chosen to have
the Planck constant and particle mass equal one: ប⫽m⫽1.
A. Example 1: Tunneling escape from a metastable
state
The first applications of QHD models decay of a meta-
stable state.44,46 At low energies the decay is due to tunneling
through the potential barrier. Examples of such processes are
numerous in chemistry and range from dissociation of elec-
tronically excited states of small molecules in gas phase9 to
biochemical processes such as enzyme mediated proton or
proton-coupled electron transfer10,40 and isomerization
reactions.67 Dynamical tunneling68 can provide important
contributions to the decay process even at high energies in
competition with classically accessible pathways. The one
dimensional Hamiltonian of the metastable state is defined
by
p2 q2
H 共 p,q 兲 ⫽ ⫹ ⫹aq 3 , a⫽0.1. 共18兲
2 2
It describes an oscillator with a cubic anharmonicity. The
potential energy function is plotted in Fig. 1.
The QHD approach is applied to second order. The QHD
set of variables includes momentum and position as in clas-
sical mechanics, together with the squares of momentum,
position and the symmetrized cross term. The set contains
five variables:
具 A 典 ⬅ 兵 具 P̂ 典 , 具 Q̂ 典 , 具 P̂ 2 典 , 具 Q̂ 2 典 , 具 P̂Q̂ 典 s 其 , 共19兲
compared to two variables in classical mechanics. Closure of
the third and higher order terms results in the following
EOM:
J. Chem. Phys., Vol. 113, No. 16, 22 October 2000 Quantized Hamilton dynamics 6561

FIG. 2. Trajectory of the metastable particle in the tunneling example. FIG. 3. Phase space evolution of the metastable particle in the tunneling
共a兲 具 Q̂ 典 (t⫽0)⫽1, 具 P̂ 典 (t⫽0)⫽⫺1, 具 E 典 ⫽1.75; 共b兲 具 Q̂ 典 (t⫽0)⫽⫺1, example. The notation is the same as in Fig. 2.
具 P̂ 典 (t⫽0)⫽1, 具 E 典 ⫽1.25. The quantum, classical and QHD trajectories are
given by thick solid, thin solid, and dashed lines, respectively.

bracket of Step 3 of the QHD algorithm and the closure

d 具 Q̂ 典 procedure of Step 4 are unique to QHD and make it directly
⫽ 具 P̂ 典 , 共20兲
dt extendible to higher orders. The dynamics of the QHD
EOMs obtained to any order has another unique property due
d 具 P̂ 典 to the closure procedure of Step 4 of the QHD algorithm. In
⫽⫺ 具 Q̂ 典 ⫺3a 具 Q̂ 2 典 , 共21兲
dt the classical limit ប⫽0 with classical initial conditions for
the QHD variables, i.e., 具 Q̂ 2 典 ⫽ 具 Q̂ 典具 Q̂ 典 , etc., the QHD dy-
d 具 Q̂ 2 典 namics for the extended set of variables is identical to the
⫽2 具 P̂Q̂ 典 s , 共22兲
dt corresponding Hamilton dynamics for these variables. To-
gether with the energy conservation property discussed be-
d 具 P̂ 2 典 low, this property provides a useful test of QHD codes.
⫽⫺2 具 P̂Q̂ 典 s ⫺6a 共 2 具 P̂Q̂ 典 s 具 Q̂ 典 ⫹ 具 P̂ 典具 Q̂ 2 典
dt As follows from the Hamiltonian 共18兲, the total energy
of the metastable system is given in the second order QHD
⫺2 具 P̂ 典具 Q̂ 典 2 兲 , 共23兲 approach by
d 具 P̂Q̂ 典 s
⫽ 具 P̂ 2 典 ⫺ 具 Q̂ 2 典 ⫺3a 共 3 具 Q̂ 2 典具 Q̂ 典 ⫺2 具 Q̂ 典 3 兲 . 共24兲
dt 具 P̂ 2 典 具 Q̂ 2 典
具E典⫽ ⫹ ⫹a 共 3 具 Q̂ 2 典具 Q̂ 典 ⫺2 具 Q̂ 典 3 兲 , 共25兲
2 2
The derivation is described in the Appendix.
As pointed out in the review process, the second order where the anharmonic term is expressed using the available
QHD EOMs are reminiscent of the equations obtained by variables 共19兲 according to Eq. 共12兲. The total energy is con-
Heller19 and Mukamel.18 Both Heller’s and Mukamel’s ap- served during the evolution by Eqs. 共20兲–共24兲. The initial
proaches are based on the Gaussian ansatz for the quantum- quantum mechanical wave function is a Gaussian wave
mechanical wave function and Wigner distribution function packet, Eq. 共17兲. The center p 0 , q 0 of the wave packet de-
and produce dynamics that is different from QHD. For in- fines the initial conditions of the classical simulation. The
stance, the 具 P̂ 典 and 具 Q̂ 典 variables in Ref. 19 evolve purely initial conditions in QHD are the quantum mechanical aver-
classically and, therefore, do not tunnel. QHD does not re- ages from the set 共19兲 taken with respect to the the Gaussian
quire the Gaussian ansatz. The mixed quantum-classical wave packet 共17兲,
6562 J. Chem. Phys., Vol. 113, No. 16, 22 October 2000 O. V. Prezhdo and Y. V. Pereverzev

具 Q̂ 典 t⫽0 ⫽q 0 , 具 P̂ 典 t⫽0 ⫽p 0 ,
ប
具 Q̂ 2 典 t⫽0 ⫽q 20 ⫹ ,
2m ␻
共26兲
mប ␻
具 P̂ 2 典 t⫽0 ⫽p 20 ⫹ ,
2

具 P̂Q̂ 典 s,t⫽0 ⫽p 0 q 0
with ប⫽m⫽ ␻ ⫽1.
The results of the quantum-mechanical, classical and
QHD simulations are presented in Figs. 2 and 3. The evolu-
tion of classical position and momentum is compared with
the evolution of the corresponding QHD variables and the
average values from the quantum simulations. Figure 2
shows time dependence of coordinate. Figure 3 shows mo-
mentum vs position in the phase space. Two sets of initial
conditions are considered. The trajectories in Figs. 2共a兲 and
3共a兲 originate on the right slope of the pseudoharmonic re-
gion, Fig. 1, with momentum to the left. The trajectories in
Figs. 2共b兲 and 3共b兲 originate on the left slope with momen-
tum to the right. Quantum mechanically, any state localized
inside the pseudoharmonic region of the potential is meta-
stable and will decay in time. Classically, only particles with
the total energy higher than the energy of the barrier can
escape. In both 共a兲 and 共b兲 cases the classical trajectories are FIG. 4. Deep tunneling QHD evolution of the metastable particle. The ini-
periodic and are not able to reproduce the quantum mechani- tial conditions are 具 Q̂ 典 (t⫽0)⫽0, 具 P̂ 典 (t⫽0)⫽1.05 and the total QHD en-
cal decay of the metastable state. Second order QHD cor- ergy is 具 E 典 ⫽1.051 25.
rectly describes the tunneling escape in both cases. The QHD
trajectory starting at q 0 ⫽1 is higher in energy and more
strong intermode coupling usually leads to faster reactions.
closely agrees with the quantum mechanical data than the
Efficient energy exchange between modes is the necessary
trajectory starting at q 0 ⫽⫺1.
condition for applicability of transition state theories. In pho-
Similar to classical mechanics, QHD exhibits a threshold
tochemistry, direct excitation of the reactive mode decays by
energy below which the nature of the dynamics changes.
coupling to other modes and the reaction is slowed down.
Formation of the cusp in Fig. 3共b兲 indicates that the q 0
Energy exchange is significantly influenced by ZPE which
⫽⫺1 trajectory is getting close to the threshold. The thresh-
comprises a large fraction of energy stored in high frequency
old energy is notably less in second order QHD than in clas-
modes. At room temperature, high frequency modes involve
sical mechanics and can be decreased by extension of the
not only the low mass C–H and O–H vibrations, but also
closure procedure to higher orders. In contrast to the classical
C–C, C–O, C–N and other bonds.
motion which for the present model is periodic below the
The Hamiltonian of the ZPE model is a simplified ver-
threshold energy, the QHD dynamics becomes chaotic below
sion of the well-known Henon–Heiles Hamiltonian44,69,70
the corresponding threshold.69 An example of a chaotic tra-
jectory is given in Fig. 4. Here, tunneling is deep and takes p 21 ␻ 21 q 21 p 22 ␻ 22 q 22
place after many oscillations inside the well. The trajectory H 共 p 1 ,q 1 ,p 2 ,q 2 兲 ⫽ ⫹ ⫹ ⫹ ⫹␭q 1 q 22
2 2 2 2
suggests that deep quantum mechanical tunneling is repre- 共27兲
sented in QHD by a chaotic motion in the extended phase
space. The QHD trajectory explores the extended phase ␻ 1 ⫽1.0, ␻ 2 ⫽1.1, ␭⫽⫺0.11.
space, finds the tunneling bottleneck and escapes. The parameters of the model are the same as in Ref. 44.
Similar to the previous example, QHD is developed to sec-
ond order in each degree of freedom. In addition to the mo-
B. Example 2: ZPE and energy exchange between
two oscillators menta and coordinates of the two modes 具 P̂ 1 典 , 具 Q̂ 1 典 , and
具 P̂ 2 典 , 具 Q̂ 2 典 that are present in classical mechanics, six new
The second model system illustrates the effect of zero variables are added. These are the squares of position and
point motion in energy exchange between two harmonic os-
momentum 具 P̂ 21 典 , 具 Q̂ 21 典 , 具 P̂ 22 典 , 具 Q̂ 22 典 and the symmetrized
cillators coupled by an anharmonic term. Energy exchange
has wide implications in chemistry. Chemical reaction rates position-momentum correlations 具 P̂ 1 Q̂ 1 典 s ⫽ 具 ( P̂ 1 Q̂ 1
are determined by the amount of energy stored in the reac- ⫹Q̂ 1 P̂ 1 )/2典 , 具 P̂ 2 Q̂ 2 典 s ⫽ 具 ( P̂ 2 Q̂ 2 ⫹Q̂ 2 P̂ 2 )/2典 . The cross-
tive mode. In thermally activated reactions where the energy terms between the modes such as P̂ 1 P̂ 2 , P̂ 1 Q̂ 2 , etc., are
reaches the reactive mode through coupling to a heat bath, neglected. If included, the cross terms would dominate QHD
J. Chem. Phys., Vol. 113, No. 16, 22 October 2000 Quantized Hamilton dynamics 6563

variable sets in large systems. Decomposition of such terms

into products of first order classical terms significantly im-
proves dimensionality scaling of the method. The total of 10
QHD variables in the present calculation should be com-
pared with the total of four classical variables.
The QHD EOMs are derived using the closure procedure
described earlier. The cubic terms are decomposed using Eq.
共12兲. The cross-terms of the type 具 P̂ 1 P̂ 2 典 are approximated
by the products 具 P̂ 1 典具 P̂ 2 典 . The final result is

d 具 Q̂ 1 典
⫽ 具 P̂ 1 典 , 共28兲
dt
FIG. 5. Harmonic mode energies 共40兲 as functions of time in the ZPE
d 具 Q̂ 2 典 example. Thick, thin solid, and dashed lines depict the energies calculated
⫽ 具 P̂ 2 典 , 共29兲 quantum mechanically, classically, and by QHD, respectively.
dt

d 具 P̂ 1 典
⫽⫺ ␻ 21 具 Q̂ 1 典 ⫺␭ 具 Q̂ 22 典 , 共30兲 where i⫽1,2, and n i ⫽0 refers to the initial quantum state of
dt
the ith oscillator. The values of the angle variables ␾ i are
d 具 P̂ 2 典 selected randomly in the interval 共0,2␲兲.
⫽⫺ ␻ 22 具 Q̂ 2 典 ⫺2␭ 具 Q̂ 1 典具 Q̂ 2 典 , 共31兲 The dynamical quantities of interest are the the harmonic
dt mode energies defined by
d 具 Q̂ 21 典 具 P̂ 2i 典
␻ 2i 具 Q̂ 2i 典
⫽2 具 P̂ 1 Q̂ 1 典 s , 共32兲 具 E i典 ⫽ ⫹ , i⫽1,2. 共40兲
dt 2 2

d 具 Q̂ 22 典 The quantum mechanical expectation values are computed

⫽2 具 P̂ 2 Q̂ 2 典 s , 共33兲 with respect to the evolving wave packet. The harmonic
dt
mode energies in the QHD approach are given by the 具 P̂ 2i 典
d 具 P̂ 21 典 and 具 Q̂ 2i 典 variables. Classically, the mode energies are cal-
⫽⫺2 ␻ 21 具 P̂ 1 Q̂ 1 典 s ⫺2␭ 具 Q̂ 1 典具 Q̂ 22 典 , 共34兲 culated by averaging over an ensemble of 1500 trajectories
dt
initiated using different random numbers ␾ i , Eq. 共39兲. The
d 具 P̂ 22 典 results are presented in Fig. 5. A substantial disagreement is
⫽⫺2 ␻ 22 具 P̂ 2 Q̂ 2 典 s ⫺4␭ 具 Q̂ 1 典具 P̂ 2 Q̂ 2 典 s , 共35兲 observed between the quantum and classical results due to
dt
the ZPE effect. Classically, the energy is free to flow from
d 具 P̂ 1 Q̂ 1 典 s one mode to the other. At long times the energy can concen-
⫽ 具 P̂ 21 典 ⫺ ␻ 21 具 Q̂ 21 典 ⫺␭ 具 Q̂ 1 典具 Q̂ 22 典 , 共36兲 trate in a single mode. The classical energy flow is more
dt chaotic and with a larger amplitude in a single trajectory and
is smoothed in Fig. 5 by the ensemble averaging. Quantum
d 具 P̂ 2 Q̂ 2 典 s
⫽ 具 P̂ 22 典 ⫺ ␻ 22 具 Q̂ 22 典 ⫺2␭ 具 Q̂ 1 典具 Q̂ 22 典 . 共37兲 mechanically, each mode has to contain ZPE. Consequently,
dt the quantum mechanical energy exchange is significantly
The second order QHD expression for the total energy is weaker compared to the flow of the classical energy. QHD
obtained by decomposing the cubic term in the Hamiltonian reproduces the quantum mechanical behavior. The harmonic
共27兲 mode energies do not decrease below ZPE. The QHD com-
putational effort is roughly 2.5 of the computational effort
具 P̂ 21 典 ␻ 21 具 Q̂ 21 典 具 P̂ 22 典 ␻ 22 具 Q̂ 22 典 for a single classical trajectory. This is at least two orders of
具E典⫽ ⫹ ⫹ ⫹ ⫹␭ 具 Q̂ 1 典具 Q̂ 22 典 . magnitude better than for the ensemble of classical trajecto-
2 2 2 2
共38兲 ries and about four orders better than for the full quantum
simulation.
The initial conditions represent the product of the ground
state wave functions of each harmonic mode. The ground
state quantum wave packet of the harmonic oscillator is IV. CONCLUSIONS
given by Eq. 共17兲 with q 0 ⫽p 0 ⫽0. The QHD initial condi- The QHD formalism presented in the paper establishes a
tions are given by Eqs. 共26兲 for each mode. The initial con- natural extension of classical Hamilton dynamics. It provides
ditions for the classical trajectories are selected in the usual efficient means to incorporate quantum effects such as tun-
way44 to correspond to the harmonic potential expressed in neling and ZPE into classical calculations. The variables rep-
the action-angle variables resenting the quantum effects are treated on equal footing
q i,t⫽0 ⫽ 冑共 2n i ⫹1 兲 ប/ ␻ i sin ␾ i , with the classical position and momentum variables. In the
共39兲 lowest order, QHD is equivalent to classical mechanics.
p i,t⫽0 ⫽ 冑共 2n i ⫹1 兲 ប ␻ i cos ␾ i , QHD approaches the exact quantum limit when the QHD
6564 J. Chem. Phys., Vol. 113, No. 16, 22 October 2000 O. V. Prezhdo and Y. V. Pereverzev

hierarchy of equations is extended to higher orders. Due to which is the same as Eq. 共24兲. The EOM of the new dynami-
flexibility of the QHD formalism, quantum effects can be cal variable 具 P̂Q̂ 典 s is
incorporated into a classical calculation in a systematic man-
ner and to any desired degree of accuracy. As exemplified by d 具 P̂Q̂ 典 s
i ⫽ 具 关共 P̂Q̂⫹Q̂ P̂ 兲 /2,Ĥ 兴 典
the model applications, the lowest order QHD approximation dt
that goes beyond classical mechanics already gives a dra-
matic improvement over the purely classical theory. The ⫽⫺i 具 Q̂ 2 典 ⫺i3a 具 Q̂ 3 典 ⫹i 具 P̂ 2 典 . 共A3兲
computational cost of the lowest order QHD is extremely It spawns two more variables 具 P̂ 典 and 具 Q̂ 典 . P̂ belongs to
2 3 2
modest and is only 3 times greater than that of a classical the set 共19兲 and is also treated as an independent variable
calculation. with the EOM
Due to its formal consistency and computational effi-
ciency, the QHD approach deserves further exploration. De- d 具 P̂ 2 典
composition of the Hamiltonian 共4兲 into the quantum and i ⫽ 具 关 P̂ 2 ,Ĥ 兴 典 ⫽⫺i2 具 P̂Q̂ 典 s ⫺i3a 具 P̂Q̂ 2 ⫹Q̂ 2 P̂ 典 .
dt
classical parts is not unique and can be optimized depending 共A4兲
on application. The closure procedure that terminates the hi-
erarchy of QHD EOM should be tested with more general The variables 具 Q̂ 3 典 and 具 P̂Q̂ 2 ⫹Q̂ 2 P̂ 典 , however, do not be-
potentials. Various extensions of the basic QHD algorithm long to the set 共19兲. The hierarchy of equations is terminated
are possible, for example, to systems with separate quantum at these variables, which are approximated according to Eq.
and classical modes as well as to non-adiabatic systems that 共12兲 by
evolve on several potential energy surfaces. Similar to clas- 具 Q̂ 3 典 ⫽3 具 Q̂ 2 典具 Q̂ 典 ⫺2 具 Q̂ 典 3 共A5兲
sical molecular dynamics, QHD can be employed in statisti-
60
cal mechanical studies of equilibrium and nonequilibrium and, with proper symmetrization,
properties of matter. Statistical mechanical applications of
具 P̂Q̂ 2 ⫹Q̂ 2 P̂ 典 ⫽4 具 Q̂ 典具 P̂Q̂ 典 s ⫺4 具 P̂ 典具 Q̂ 典 2 ⫹2 具 P̂ 典具 Q̂ 2 典 .
QHD will require coupling of the deterministic quantized 共A6兲
dynamics with a heat or pressure bath. Last, but not the least,
the formal group theoretical foundations of QHD should be Equations 共A5兲 and 共A6兲 combined with Eqs. 共A3兲 and 共A4兲
investigated. As it presently stands, QHD is a consistent dy- give Eqs. 共23兲 and 共24兲.
namical theory of quantum effects and is close to classical
Hamilton mechanics both in formal spirit and computational 1
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