Real-time propagation of time-dependent density-functional theory plus U for non-adiabatic electron transitions in electron-atom coupled motions

Abstract

To calculate non-adiabatic electron transition phenomena, for which electronic and atomic motions are coupled and thus the Born-Oppeheimer approximation is not validated, we implemented the real-time time-dependent density functionals theory through the Szuki-Trotter’s splitting time propagator. In order to compensate the chronic over-delocalization error of the local multiplicative local-operator density functionals, the Hubbard U potential is added in line with other non-local components in the Szuki-Trotter’s splitting scheme. We present a few model systems, in which the molecular structures cross over to a different branch of potential energy surface defined by a U term.