Electronic absorption spectra from off-diagonal quantum master equations

Abstract

Quantum master equations (QMEs) provide a general framework for describing electronic dynamics within a complex molecular system. Off-diagonal QMEs (OD-QMEs) correspond to a family of QMEs that describe the electronic dynamics in the interaction picture based on treating the off-diagonal coupling terms between electronic states as a small perturbation within the framework of second-order perturbation theory. The fact that OD-QMEs are given in terms of the interaction picture makes it non-trivial to obtain Schrödinger picture electronic coherences from them. A key experimental quantity that relies on the ability to obtain accurate Schrödinger picture electronic coherences is the absorption spectrum. In this paper, we propose using a recently introduced procedure for extracting Schrödinger picture electronic coherences from interaction picture inputs to calculate electronic absorption spectra from the electronic dynamics generated by OD-QMEs. The accuracy of the absorption spectra obtained this way is studied in the context of a biexciton benchmark model, by comparing spectra calculated based on time-local and time-nonlocal OD-QMEs to spectra calculated based on a Redfield-type QME and the non-perturbative and quantum-mechanically exact hierarchical equations of motion method.