D. Kohen et Dj. Tannor, CLASSICAL-QUANTUM CORRESPONDENCE IN THE REDFIELD EQUATION AND ITS SOLUTIONS, The Journal of chemical physics, 107(13), 1997, pp. 5141-5153
In a recent paper we showed the equivalence, under certain well-charac
terized assumptions, of Redfield's equations for the density operator
in the energy representation with the Gaussian phase space ansatz for
the Wigner function of Yan and Mukamel. The equivalence shows that the
solutions of Redfield's equations respect a striking degree of classi
cal-quantum correspondence, Here we use this equivalence to derive ana
lytic expressions for the density matrix of the harmonic oscillator in
the energy representation without making the almost ubiquitous secula
r approximation. From the elements of the density matrix in the energy
representation we derive analytic expressions for Gamma(1)(n)(1/T-1(n
)) and Gamma(2)(nm)(1/T-2(nm)), i.e., population and phase relaxation
rates for individual matrix elements in the energy representation. Our
results show that Gamma(1)(n)(t) = Gamma(1)(t) is independent of n; t
his is contrary to the widely held belief that Gamma(1)(n) is proporti
onal to n. We also derive the simple result that Gamma(2)(nm)(t) = \n-
m\Gamma(1)(t)/2, a generalization of the two-level system result Gamma
(2) = Gamma(1)/2. We show that Gamma(1)(t) is the classical rate of en
ergy relaxation, which has periodic modulations characteristic of the
classical damped oscillator; averaged over a period Gamma(t) is direct
ly proportional to the classical friction, gamma. An additional elemen
t of classical-quantum correspondence concerns the time rate of change
of the phase of the off diagonal elements of the density matrix, omeg
a(nm), a quantity which has received little attention previously. We f
ind that omega(nm) is time-dependent, and equal to \n - m\Omega(t), wh
ere Omega(t) is the rate of change of phase space angle in the classic
al damped harmonic oscillator. Finally, expressions for a collective G
amma(1)(t) and Gamma(2)(t) are derived, and shown to satisfy the relat
ionship Gamma(2) = Gamma(1)/2. This familiar result, when applied to t
hese collective rate constants, is seen to have a simple geometrical i
nterpretation in phase space. (C) 1997 American Institute of Physics.