Polaritonic effects in the vibronic spectrum of molecules in an optical cavity.

ABSTRACT

We present a new computational framework to describe polaritons, which treats photons and electrons on the same footing using coupled-cluster theory. As a proof of concept, we study the coupling between the first electronically excited state of carbon monoxide and an optical cavity. In particular, we focus on how the interaction with the photonic mode changes the vibrational spectroscopic signature of the electronic state and how this is affected when tuning the cavity frequency and the light-matter coupling strength. For this purpose, we consider different methodologies and investigate the validity of the Born-Oppenheimer approximation in such situations.