Non-adiabatic dynamics of molecules in optical cavities

TL;DR

This paper develops a formalism for simulating non-adiabatic molecular dynamics in optical cavities, incorporating quantum effects of the cavity field to explore modified photochemical pathways.

Contribution

It introduces a method to calculate non-adiabatic couplings for molecules in strong coupling regimes using quantum chemistry data, enabling wave packet simulations in dressed states.

Findings

Modified potential energy surfaces in cavity environments.

Altered photochemical reaction pathways.

Demonstrated formalism on model molecular systems.

Abstract

Strong coupling of molecules to the vacuum field of micro cavities can modify the potential energy surfaces opening new photophysical and photochemical reaction pathways. While the influence of laser fields is usually described in terms of classical field, coupling to the vacuum state of a cavity has to be described in terms of dressed photon-matter states (polaritons) which require quantized fields. We present a derivation of the non-adiabatic couplings for single molecules in the strong coupling regime suitable for the calculation of the dressed state dynamics. The formalism allows to use quantities readily accessible from quantum chemistry codes like the adiabatic potential energy surfaces and dipole moments to carry out wave packet simulations in the dressed basis. The implications for photochemistry are demonstrated for a set of model systems representing typical situations found in molecules.