Trajectory Surface Hopping Nonadiabatic Molecular Dynamics with Kohn–Sham ΔSCF for Condensed-Phase Systems

Abstract

We present an efficient approach for surface hopping-based nonadiabatic dynamics in the condensed phase. For the systems studied, a restricted Kohn–Sham orbital formulation of the delta self-consistent field (ΔSCF) method was used for efficient calculation of excited electronic states. Time-dependent density functional theory (DFT) is applied to aid excited-state SCF convergence and provide guess electronic state densities. Aside from that the Landau–Zener procedure simplifies the surface hopping between electronic states. By utilizing the combined Gaussian and plane waves approach with periodic boundary conditions the method is easily applicable to full atomistic DFT simulations of condensed-phase systems and was used to study the nonradiative deactivation mechanism of photoexcited diimide in water solution.