A Walk Through the Approximations of Ab Initio Multiple Spawning

TL;DR

This paper investigates the approximations in the Ab Initio Multiple Spawning method for excited-state molecular dynamics, analyzing their effects and convergence towards exact quantum results through simulations of LiH.

Contribution

It provides a detailed analysis of the approximations in Ab Initio Multiple Spawning and their impact on simulation accuracy, including convergence behavior.

Findings

Qualitative excited-state dynamics are well captured despite crude approximations.

Corrections can improve the coupling between trajectory basis functions.

Approximations have measurable effects on observables in low-dimensional systems.

Abstract

Full Multiple Spawning offers an in principle exact framework for excited-state dynamics, where nuclear wavefunctions in different electronic states are represented by a set of coupled trajectory basis functions that follow classical trajectories. The couplings between trajectory basis functions can be approximated to treat molecular systems, leading to the Ab Initio Multiple Spawning method, which has been successfully employed to study the photochemistry and photophysics of several molecules. However, a detailed investigation of its approximations and their consequences is currently missing in the literature. In this work, we simulate the explicit photoexcitation and subsequent excited-state dynamics of a simple system, LiH, and we analyze (i) the effect of the Ab Initio Multiple Spawning approximations on different observables and (ii) the convergence of the Ab Initio Multiple Spawning results towards numerically exact quantum dynamics upon a progressive relaxation of these approximations. We show that, despite the crude character of the approximations underlying Ab Initio Multiple Spawning for this low-dimensional system, the qualitative excited-state dynamics is adequately captured, and affordable corrections can further be applied to ameliorate the coupling between trajectory basis functions.