Simulating the Excited-State Dynamics of Polaritons with Ab Initio Multiple Spawning

05 October 2023, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


Over the last decade, there has been a growth of interest in polaritonic chemistry, where the formation of hybrid light-matter states (polaritons) can alter the course of photochemical reactions. These hybrid states are created by strong coupling between molecules and photons in resonant optical cavities and can even occur in the absence of light when the molecule is strongly coupled with the electromagnetic fluctuations of the vacuum field. We present a first-principles model to simulate nonadiabatic dynamics of such polaritonic states inside optical cavities by leveraging graphical processing units (GPUs). Our first implementation of this model is specialized for a single molecule coupled to a single photon mode confined inside the optical cavity, but with any number of excited states computed using complete active space configuration interaction (CASCI) and a Jaynes-Cummings type Hamiltonian. Using this model, we have simulated the excited-state dynamics of a single salicylideneaniline (SA) molecule strongly coupled to a cavity photon with the ab initio multiple spawning (AIMS) method. We demonstrate how the branching ratios of the photo-deactivation pathways for this molecule can be manipulated by coupling to the cavity. We also show how one can stop the photoreaction from happening inside an optical cavity. Finally, we also investigate cavity-based control of the ordering of two excited states (one optically bright and the other optically dark) inside a cavity for a set of molecules where the dark and bright states are close in energy.


Excited-State Dynamics

Supplementary materials

Supporting Information
Coordinates for different molecules at the relevant geometries and some additional analysis are included.


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