Sampling effects in quantum mechanical/molecular mechanics trajectory surface hopping non-adiabatic dynamics.

Abstract

The impact of different initial conditions in non-adiabatic trajectory surface hopping dynamics within a hybrid quantum mechanical/molecular mechanics scheme is investigated. The influence of a quantum sampling, based on a Wigner distribution, a fully thermal sampling, based on classical molecular dynamics, and a quantum sampled system, but thermally equilibrated with the environment, is investigated on the relaxation dynamics of solvated fulvene after light irradiation. We find that the decay from the first singlet excited state to the ground state shows high dependency on the initial condition and simulation parameters. The three sampling methods lead to different distributions of initial geometries and momenta, which then affect the fate of the excited state dynamics. We evaluated both the effect of sampling geometries and momenta, analysing how the ultrafast decay of fulvene changes accordingly. The results are expected to be of interest to decide how to initialize non-adiabatic dynamics in the presence of the environment.This article is part of the theme issue ‘Chemistry without the Born–Oppenheimer approximation’.