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International Journal of Quantum Chemistry

On the markoffian approximation in the description of relaxation in open systems

W. C. Schfeve, J. W. Middleton

Published Jun 18, 2009• 0 citations

Abstract

Most traditional discussions of the Markoffian Born approximation of relaxation phenomena (e.g., Bloch equations) are based on the assumption of widely separated time scales in the non-Markoffian weak coupling generalized master equation. By exploiting the physically reasonable Gaussian factorization property of multitime correlation functions which enter through the system reservoir interaction, recent work has shed significant new light on the relationship between the Markoffian-Born approximation and the exact generalized master equation (GME) describing the evolution of the relaxing subsystem. Two limits for which the GME becomes the Born approximation relaxation equation arc discussed: (1) the Van Hove (λ2t) limit rigorously discussed for open systems by Davies, (2) the zero memory (white noise) suggested by Middleton—Schieve and recently discussed for open systems by Gorini—Kossakawsky and Palmer. We have outlined the proof of this limit. We then discuss the physical meaning of these two exact limits in the context of the general theory of kinetic equations of Resibois. The dominant pole contributions are isolated to all orders by means of an expansion in which the terms are in norm proportional to powers of the ratio of the time scales τc/τB where τc is the two point correlation memory time and τB the relaxation time in the Born approximation. Each of the above exact limits corresponds to the vanishing of this ratio. Comments are made on nonexponential decay.

DOI: 10.1002/qua.560120868

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Abstract Memory functions in time‐convolution Generalized Master Equations (GME) for probabilities of finding a general system (interacting by a general coupling with a true thermodynamic bath) in individual states are considered without resorting to any approximation. After taking the thermodynamic bath limit, time integrals from zero to infinite times of the memories are considered. It is argued that these integrals entering, e.g., the usual naive Markov approximation converting GME the Pauli master (PME) equations are exactly zero. This implies long‐time tails of memories (unobtainable by perturbational expansions) and slower‐than‐exponential long‐time asymptotics of relaxation.

Interaction of a small system S with a large reservoir R amounts to thermal relaxation of the reduced system density operator ρS(t). The presence of the reservoir enters the equation of motion for ρS(t) through the reservoir correlation functions fkl(τ) (defined in the text), which decay to zero for τ→∞ on a time scale τc. Commonly, this τc is much smaller than the inverse relaxation constants for the time evolution of ρS(t). Then a series of approximations can be made, which lead to a Markovian equation of motion for ρS(t). In this paper the assumption of a small reservoir correlation time is removed. The equation of motion for ρS(t) is solved, and it appears that the memory effect, due to τc≂/0, can be incorporated in a frequency dependence of the relaxation operator Γ̃(ω). Subsequently, (unequal-time) quantum correlation functions of two system operators are considered, where explicit expressions for (the Laplace transform of) the correlation functions are obtained. They involve again the relaxation operator Γ̃(ω), which accounts for the time regression. Additionally it is found that an initial-correlation operator Υ̃(ω) arises, as a consequence of the fact that the equal-time correlation functions do not factorize as ρS(t) times the reservoir density operator. It is pointed out that the frequency dependence of Γ̃(ω) and the occurrence of a nonzero T̃(ω) both arise as a result of τc≂/0, and should therefore be treated on an equal footing. Explicit evaluation of Γ̃(ω) and Υ̃(ω) shows that their matrix elements can be expressed entirely in f̃kl(ω), just as in the Markov approximation. Hence no essential complications appear if one should go beyond the limits of a small reservoir correlation time τc.

We consider the dynamics of composite quantum systems in the particular case that the state operator relaxes towards the Born approximation. For this we augment the von Neumann equation by a relaxation operator imposing a finite relaxation time ${\ensuremath{\tau}}_{r}$. Under the premise that the relaxation is the dominant process we obtain a hierarchy of non-Markovian master equations. The latter arises from an expansion of the total state operator in powers of the relaxation time ${\ensuremath{\tau}}_{r}$. In the Born-Markov limit ${\ensuremath{\tau}}_{r}\ensuremath{\rightarrow}0$ the Lindblad master equation is recovered. Higher-order contributions enable a systematic treatment of correlations and non-Markovian dynamics in a recursive manner.

In this paper, we examine the validity of the Markovian approximation and the slippage scheme used to incorporate short time transient memory effects in the Markovian master equations (Redfield equations). We argue that for a bath described by a spectral function, J(omega), that is dense and smoothly spread out over the range omega(d), a time scale of tau(b) approximately 1/omega(d) exists; for times of t > tau(b), the Markovian approximation is applicable. In addition, if J(omega) decays to zero reasonably fast in both the omega --> 0 and omega --> infinity limits, then the bath relaxation time, tau(b), is determined by the width of the spectral function and is weakly dependent on the temperature of the bath. On the basis of this criterion of tau(b), a scheme to incorporate transient memory effects in the Markovian master equation is suggested. Instead of using slipped initial conditions, we propose a concatenation scheme that uses the second-order perturbation theory for short time dynamics and the Markovian master equation at long times. Application of this concatenation scheme to the spin-boson model shows that it reproduces the reduced dynamics obtained from the non-Markovian master equation for all parameters studied, while the simple slippage scheme breaks down at high temperatures.