Combining the generalized quantum master equation approach with quasiclassical mapping Hamiltonian methods to simulate the dynamics of electronic coherences.

The generalized quantum master equation (GQME) approach provides a powerful general-purpose framework for simulating the inherently quantum mechanical dynamics of a subset of electronic reduced density matrix elements of interest in complex molecular systems. Previous studies have found that combining the GQME approach with quasiclassical mapping Hamiltonian (QC/MH) methods can dramatically improve the accuracy of electronic populations obtained via those methods. In this paper, we perform a complimentary study of the advantages offered by the GQME approach for simulating the dynamics of electronic coherences, which play a central role in optical spectroscopy, quantum information science, and quantum technology. To this end, we focus on cases where the electronic coherences predicted for the spin-boson benchmark model by direct application of various QC/MH methods are inaccurate. We find that similar to the case of electronic populations, combining the QC/MH methods with the GQME approach can dramatically improve the accuracy of the electronic coherences obtained via those methods. We also provide a comprehensive analysis of how the performance of GQMEs depends on the choice of projection operator and electronic basis and show that the accuracy and feasibility of the GQME approach can benefit from casting the GQME in terms of the eigen-basis of the observable of interest. [ABSTRACT FROM AUTHOR]