Quasi-Diabatic Scheme for Non-adiabatic On-the-fly Simulations

We use the quasi-diabatic (QD) propagation scheme to perform on-the-fly non-adiabatic simulations of the photodynamics of ethylene. The QD scheme enables a seamless interface between accurate diabatic-based quantum dynamics approaches and adiabatic electronic structure calculations, explicitly avoiding any efforts to construct global diabatic states or reformulate the diabatic dynamics approach to the adiabatic representation. Using diabatic dynamics methods, the QD propagation scheme enables direct non-adiabatic simulation with complete active space self-consistent field on-the-fly electronic structure calculations. The population dynamics obtained from both approaches are in a close agreement with the quantum wavepacket based method and outperform the widely used trajectory surface hopping approach. Further analysis of the ethylene photo-deactivation pathways demonstrates the correct predictions of competing processes of non-radiative relaxation mechanism through various conical intersections. This work provides the foundation of using accurate diabatic dynamics approaches and on-the-fly adiabatic electronic structure information to perform ab-initio non-adiabatic simulation.