Diabatic couplings for charge recombination via Boys localization and spin-flip configuration interaction singles

Abstract

We describe a straightforward technique for obtaining diabatic couplings applicable to charge transfer from or charge recombination to the electronic ground state. Our method is nearly black box, requiring minimal chemical intuition from the user, and merges two well-established approaches in electronic structure theory: first, smooth and balanced adiabatic states are generated using spin-flip-configuration interaction singles (SF-CIS) based on a triplet HF state; second, Boys localization is applied to rotate all adiabatic states into charge-localized diabatic states. The method is computationally inexpensive, scaling only with the cost of CIS, and does not require a choice of active space, which is usually required for such intrinsically multiconfigurational problems. Molecular LiF in vacuum and LiF solvated by a single water molecule are examined as model systems. We find nearly smooth diabatic potential energy surfaces and couplings and we find that the Condon approximation is obeyed approximately for this model problem.