Benchmarking mixed quantum-classical molecular dynamics for electronic strong coupling.

Abstract

Experiments indicate that collective coupling of molecular ensembles to confined optical modes can modify excited-state dynamics and photochemical reactivity. To describe such cavity-induced effects at atomic resolution, semi-classical molecular dynamics approaches have been developed that treat nuclear motion classically while describing the collective light-matter interaction within the Tavis-Cummings framework of quantum electrodynamics. Here, we benchmark mixed quantum-classical approaches, Ehrenfest dynamics, and Fewest-Switches Surface Hopping (FSSH) for simulating nonadiabatic dynamics of electronically strongly coupled carbon monoxide molecules. Their predictions are compared against numerically exact quantum dynamics simulations performed with the multi-configuration time-dependent Hartree method, which treats both electronic and nuclear degrees of freedom quantum mechanically. We find that the semi-classical approaches reproduce the qualitative features of the full quantum dynamics. Quantitative agreement is best achieved with FSSH when a decoherence correction is included. These results demonstrate that mixed quantum-classical methods provide a computationally efficient and quantitatively reliable alternative to fully quantum simulations for investigating nonadiabatic photochemistry under collective electronic strong coupling in systems beyond the reach of exact quantum treatments.