<i>Ab initio</i> spin-mapping non-adiabatic dynamics simulations of photochemistry

Abstract

We perform on-the-fly non-adiabatic molecular dynamics simulations using the recently developed spin-mapping formalism. Two quantum dynamics approaches based on this mapping formalism, (i) the fully linearized Spin-LSC and (ii) the partially linearized Spin-PLDM, are explored using the quasi-diabatic propagation scheme. We have performed dynamics simulations in four ab initio molecular models for which benchmark ab initio multiple spawning (AIMS) data have been published. We find that the spin-LSC and the previously reported symmetric quasi-classical (SQC) approaches provide nearly equivalent population dynamics. While we expected the more involved spin-PLDM method to provide superior accuracy compared to the other mapping-based approaches, SQC and spin-LSC, we found that it performed with equivalent accuracy compared to the AIMS benchmark results. We further explore the underpinnings of the spin-PLDM correlation function by decomposing its N2 density matrix-focused initial conditions, where N is the number of states in the quantum subsystem. Finally, we found an approximate form of the spin-PLDM correlation function, which simplifies the simulation and reduces the computational costs from N2 to N.