From Many-Body Ab Initio to Effective Excitonic Models: A Versatile Mapping Approach Including Environmental Embedding Effects

Abstract

We present an original multistate projective diabatization scheme based on Green’s function formalisms that allows the systematic mapping of many-body ab initio calculations onto effective excitonic models. This method inherits the ability of the Bethe–Salpeter equation to describe Frenkel molecular excitons and intermolecular charge-transfer states equally well, as well as the possibility for an effective description of environmental effects in a QM/MM framework. The latter is found to be a crucial element in order to obtain accurate model parameters for condensed phases and to ensure their transferability to excitonic models for extended systems. The method is presented through a series of examples illustrating its quality, robustness, and internal consistency.