Multi-state formulation of the frozen-density embedding quasi-diabatization approach.

Abstract

We present a multi-state implementation of the recently developed frozen-density embedding diabatization (FDE-diab) methodology [D. G. Artiukhin and J. Neugebauer, J. Chem. Phys. 148, 214104 (2018)] in the Serenity program. The new framework extends the original approach such that any number of charge-localized quasi-diabatic states can be coupled, giving an access to calculations of ground and excited state spin-density distributions as well as to excitation energies. We show that it is possible to obtain results similar to those from correlated wave function approaches such as the complete active space self-consistent field method at much lower computational effort. Additionally, we present a series of approximate computational schemes, which further decrease the overall computational cost and systematically converge to the full FDE-diab solution. The proposed methodology enables computational studies on spin-density distributions and related properties for large molecular systems of biochemical interest.