Derivative couplings and analytic gradients for diabatic states, with an implementation for Boys-localized configuration-interaction singles

Abstract

We demonstrate that Boys-localized diabatic states do indeed exhibit small derivative couplings, as is required of quasidiabatic states. In doing so, we present a general formalism for calculating derivative couplings and analytic gradients for diabatic states. We then develop additional equations specific to the case of Boys-localized configuration-interaction singles (CIS) - in particular, the analytic gradient of the CIS dipole matrix - and we validate our implementation against finite-difference results. In a forthcoming paper, we will publish additional algorithmic and computational details and apply our method to the Closs energy-transfer systems as a further test of the validity of Boys-localized diabatic states. © 2013 AIP Publishing LLC.