Global Switch Trajectory Surface Hopping Dynamics in the Framework of Time-Dependent Density Functional Theory

Abstract

The mixed quantum-classical molecular dynamics methods have been employed in nonadiabatic molecular dynamics simulations for relatively larger systems, and trajectory surface hopping (TSH) based molecular dynamics method is one of the most important strategy to study nonadiabatic photophysical and photochemical processes for large complex chemical systems. This chapter introduces the GS-TSH method based on Zhu-Nakamura formula for general two-state curve crossing problem, and focuses on its applications and performances especially in the framework of time-dependent density functional theory. This method could yield an accurate description of the nonadiabatic molecular dynamics simulation at low computational cost. In particular, the use of well-defined classical trajectories and switching probabilities in the GS algorithm make it possible to employ direct dynamics, i.e., an on-the-fly approach where only potential energy surfaces and its gradients are required to be calculated at each point of time along running trajectory.