Optimal diabatic states based on solvation parameters

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