Impact of Cavity on Molecular Ionization Spectra

TL;DR

This paper explores how optical cavities influence molecular ionization spectra, revealing that cavity-induced effects can significantly alter spectra, especially in less symmetric molecules, through dynamical symmetry breaking and orientation control.

Contribution

It demonstrates that cavities can strongly affect molecular ionization spectra by inducing symmetry breaking and coupling vibrational modes previously considered irrelevant.

Findings

Cavity presence significantly alters ionization spectra.

Molecular symmetry and orientation control the cavity effects.

Less symmetric molecules show greater spectral modifications.

Abstract

Ionization phenomena are widely studied for decades. With the advent of cavity technology, the question arises how quantum light affects molecular ionization. As the ionization spectrum is recorded from the neutral ground state, it is usually possible to choose cavities which exert negligible effect on the neutral ground state, but have significant impact on the ion and the ionization spectrum. Particularly interesting are cases where the ion exhibits conical intersections between close-lying electronic states, which gives rise to substantial nonadiabatic effects. Assuming single-molecule strong coupling, we demonstrate that vibrational modes irrelevant in the absence of cavity play a decisive role when the molecule is in the cavity. Here, dynamical symmetry breaking is responsible for the ion-cavity coupling and high symmetry enables control of the coupling via molecular orientation relative to the cavity field polarization. Significant impact on the spectrum by the cavity is found and shown to even substantially increase for less symmetric molecules.