Nonperturbative non-Markovian quantum master equation: Validity and limitation to calculate nonlinear response functions

Based on the influence functional formalism, we have derived a nonperturbative equation of motion for a reduced system coupled to a harmonic bath with colored noise in which the system-bath coupling operator does not necessarily commute with the system Hamiltonian. The resultant expression coincides with the time-convolution less quantum master equation derived from the second-order perturbative approximation, which is also equivalent to a generalized Redfield equation. This agreement occurs because, in the nonperturbative case, the relaxation operators arise from the higher-order system-bath interaction that can be incorporated into the reduced density matrix as the influence operator; while the second-order interaction remains as a relaxation operator in the equation of motion. While the equation describes the exact dynamics of the density matrix beyond weak system-bath interactions, it does not have the capability to calculate nonlinear response functions appropriately. This is because the equation cannot describe memory effects which straddle the external system interactions due to the reduced description of the bath. To illustrate this point, we have calculated the third-order two-dimensional (2D) spectra for a two-level system from the present approach and the hierarchically coupled equations approach that can handle quantal system-bath coherence thanks to its hierarchical formalism. The numerical demonstration clearly indicates the lack of the system-bath correlation in the present formalism as fast dephasing profiles of the 2D spectra. (c) 2007 Elsevier B.V. All rights reserved.