Probing the sensitivity of ab initio multiple spawning to its parameters

Abstract

AbstractFull multiple spawning (FMS) offers a strategy to simulate the nonadiabatic dynamics of molecular systems by describing their nuclear wavefunctions by a linear combination of coupled trajectory basis functions (TBFs). Applying a series of controlled approximations to the full multiple spawning (FMS) equations leads to theab initiomultiple spawning (AIMS), which is compatible with an on-the-fly propagation of the TBFs and an accurate description of nonadiabatic processes. The AIMS strategy and its numerical implementations, however, rely on a series of user-defined parameters. Herein, we investigate the influence of these parameters on the electronic-state population of two molecular systems— trans-azomethane and a two-dimensional model of the butatriene cation. This work highlights the stability of AIMS with respect to most of its parameters, underlines the specific parameters that require particular attention from the user of the method, and offers prescriptions for an informed selection of their value.