Discrete Generalized Quantum Master Equations.

Several derivative and integral approximations are explored for discretizing the Nakajima-Zwanzig generalized quantum master equation (NZ-QME or GQME) to obtain discrete quantum master equation (DQME) hierarchies and relations between discrete memory kernel and reduced density matrix (RDM) elements. It is shown that the simplest forward-difference approximation does not allow the reliable determination of the discrete kernel elements, even in the infinitesimal time-step limit, and that discrete kernels obtained in earlier work are flawed, although the procedure can be remedied. The various approximations give rise to DQMEs that differ in structure and in the RDM-kernel relationships. It is shown that the use of a more accurate discretization based on the midpoint derivative and midpoint integral approximations leads to a DQME that exhibits endpoint effects, which reflect the weaker impact of the bath on the RDM during the first time step and which parallel those encountered in the small matrix decomposition of the path integral (SMatPI) with a symmetric factorization of the short-time propagator. The features of the DQME hierarchies and RDM-kernel relations are illustrated through analytical examples involving a simple integrodifferential equation and a scalar GQME model, as well as numerical results for a two-level system (TLS) coupled to a harmonic bath.