Ab initio molecular dynamics study of intersystem crossing dynamics for MH2 (M = Si, Ge, Sn, Pb) on spin‐pure and spin‐mixed potential energy surfaces

Abstract

AbstractRecently, surface‐hopping ab initio molecular dynamics (SH‐AIMD) simulations have come to be used to discuss the mechanisms and dynamics of excited‐state chemical reactions, including internal conversion and intersystem crossing. In dynamics simulations involving intersystem crossing, there are two potential energy surfaces (PESs) governing the motion of nuclei: PES in a spin‐pure state and PES in a spin‐mixed state. The former gives wrong results for molecular systems with large spin‐orbit coupling (SOC), while the latter requires a potential gradient that includes a change in SOC at each point, making the computational cost very high. In this study, we systematically investigate the extent to which the magnitude of SOC affects the results of the spin‐pure state‐based dynamics simulations for the hydride MH2 (M = Si, Ge, Sn, Pb) by performing SH‐AIMD simulations based on spin‐pure and spin‐mixed states. It is clearly shown that spin‐mixed state PESs are indispensable for the dynamics simulation of intersystem crossing in systems containing elements Sn and Pb from the fifth period onward. Furthermore, in addition to the widely used Tully's fewest switches (TFS) algorithm, the Zhu‐Nakamura (ZN) global switching algorithm, which is computationally less expensive, is applied to SH for comparison. The results from TFS‐ and ZN‐SH‐AIMD methods are in qualitative agreement, suggesting that the less expensive ZN‐SH‐AIMD can be successfully utilized to investigate the dynamics of photochemical reactions based on quantum chemical calculations.