Impact of dipole self-energy on cavity-induced nonadiabatic dynamics

TL;DR

This paper introduces a new method to compute the dipole self-energy in cavity quantum electrodynamics and investigates its subtle effects on nonadiabatic molecular dynamics and conical intersections.

Contribution

A novel computational approach for the dipole self-energy and an analysis of its influence on cavity-induced nonadiabatic effects in molecules.

Findings

DSE computation method developed and validated.

DSE slightly alters light-induced conical intersections.

DSE breaks symmetry of conical intersections.

Abstract

The coupling of matter to the quantized electromagnetic field of a plasmonic or optical cavity can be harnessed to modify and control chemical and physical properties of molecules. In optical cavities, a term known as the dipole self-energy (DSE) appears in the Hamiltonian to assure gauge invariance. The aim of this work is twofold. First, we introduce a method, which has its own merits and complements existing methods, to compute the DSE. Second, we study the impact of the DSE on cavity-induced nonadiabatic dynamics in a realistic system. For that purpose, various matrix elements of the DSE are computed as functions of the nuclear coordinates and the dynamics of the system after laser excitation is investigated. The cavity is known to induce conical intersections between polaritons, which gives rise to substantial nonadiabatic effects. The DSE is shown to slightly affect these light-induced conical intersections and, in particular, break their symmetry.