Optimal diabatic states based on solvation parameters

Abstract

A new method for obtaining diabatic electronic states of a molecular system in a condensed environment is proposed and evaluated. This technique, which we denote as Edmiston-Ruedenberg (ER)-ε diabatization, forms diabatic states as a linear combination of adiabatic states by minimizing an approximation to the total coupling between states in a medium with temperature T and with a characteristic Pekar factor C. ER-ε diabatization represents an improvement upon previous localized diabatization methods for two reasons: first, it is sensitive to the energy separation between adiabatic states, thus accounting for fluctuations in energy and effectively preventing over-mixing. Second, it responds to the strength of system-solvent interactions via parameters for the dielectric constant and temperature of the medium, which is physically reasonable. Here, we apply the ER-ε technique to both intramolecular and intermolecular excitation energy transfer systems. We find that ER-ε diabatic states satisfy three important properties: (1) they have small derivative couplings everywhere; (2) they have small diabatic couplings at avoided crossings, and (3) they have negligible diabatic couplings everywhere else. As such, ER-ε states are good candidates for so-called "optimal diabatic states."