Extending the Applicability of the Multiple-Spawning Framework for Nonadiabatic Molecular Dynamics

Abstract

Ab initio multiple-spawning (AIMS) describes the nonadiabatic dynamics of molecules by expanding nuclear wave functions in a basis of traveling multidimensional Gaussians called trajectory basis functions (TBFs). New TBFs can be spawned whenever nuclear amplitude is transferred between electronic states due to nonadiabatic transitions. While the adaptive size of the TBF basis grants AIMS its characteristic accuracy in describing nonadiabatic processes, it also leads to a fast and uncontrolled growth of the number of TBFs, penalizing computational efficiency. A different flavor of AIMS, called AIMS with informed stochastic selections (AIMSWISS), has recently been proposed to reduce the number of TBFs dramatically. Herein, we test the performance of AIMSWISS for a series of challenging nonadiabatic processes—photodynamics of two-dimensional model systems, 1,2-dithiane and chromium (0) hexacarbonyl—and show that this method is robust and extends the range of molecular systems that can be simulated within the multiple-spawning framework.