On-the-Fly Cavity-Molecular Dynamics of Vibrational Polaritons

TL;DR

This paper introduces a computational method combining DFTB and light-matter Hamiltonian to simulate vibrational polaritons in optical cavities, with a focus on efficiency and practical application to water spectra.

Contribution

It develops a parallelized, lightweight propagation scheme for vibrational polaritons, replacing Born charges with Mulliken charges for efficiency, and provides an open-source package CavOTF.

Findings

Mulliken charges can replace Born charges for qualitative spectra.

The approach accurately computes angle-resolved water polaritonic spectra.

Spurious heating limits the method's use for energy transport or chemical dynamics.

Abstract

In this work, we combine the density functional tight-binding (DFTB) approach with a light-matter Hamiltonian beyond the long-wavelength approximation to propagate the dynamics of vibrational polaritons formed by coupling molecular vibrations to confined radiation inside a Fabry-P\'{e}rot optical cavity. Here, we develop a parallelized propagation scheme with lightweight inter-CPU communication by exploiting the sparse nature of the light-matter interactions in the real space representation. We find that the computationally expensive Born charges required for our propagation can be replaced with the computationally inexpensive Mulliken charges to obtain qualitatively accurate linear spectra especially when the nonlinearity (arising from molecular vibrations) of the light-matter interaction term is not substantial. However, the same approach may not be suitable to be used for studying cavity modification of energy transport or chemical dynamics as this approximation leads to spurious heating of the light-matter hybrid system. We demonstrate the utility of this on-the-fly approach to compute angle resolved polaritonic spectra of water. We implement our approach as an open-source computational package, CavOTF, which is available on GitHub.