Journal of Physical Chemistry B, Vol.109, No.45, 21399-21405, 2005
Markovian approximation in the relaxation of open quantum systems
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) similar to 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.