Ab-initio Symmetric Quasi-Classical Approach to Investigate Molecular Tully Models

TL;DR

This paper evaluates the symmetric quasi-classical (SQC) approach for non-adiabatic molecular dynamics using Tully models, demonstrating significant accuracy improvements with gamma corrections and benchmarking against surface hopping methods.

Contribution

It introduces a systematic benchmarking of SQC methods with gamma corrections on Tully models, highlighting their superior accuracy over traditional surface hopping approaches.

Findings

Gamma-corrected SQC outperforms surface hopping in accuracy.

Trajectory adjustments significantly improve quantum dynamics simulations.

Benchmark results provide insights for developing new quantum dynamics methods.

Abstract

We perform on-the-fly non-adiabatic molecular dynamics simulations using the symmetrical quasi-classical (SQC) approach with the recently suggested molecular Tully models: ethylene and fulvene. We attempt to provide benchmarks of the SQC methods using both the square and the triangle windowing schemes as well as the recently proposed electronic zero-point-energy correction scheme (so-called the gamma correction). We use the quasi-diabatic propagation scheme to directly interface the diabatic SQC methods with adiabatic electronic structure calculations. Our results showcase the drastic improvement of the accuracy by using the trajectory-adjusted gamma-corrections, which outperform the widely used trajectory surface hopping method with decoherence corrections. These calculations provide useful and non-trivial tests to systematically investigate the numerical performance of various diabatic quantum dynamics approaches, going beyond simple diabatic model systems that have been used as the major workhorse in the quantum dynamics field. At the same time, these available benchmark studies will also likely foster the development of new quantum dynamics approaches based on these techniques.