Dynamic of Single Molecules in Collective Light-Matter States from First Principles

TL;DR

This paper introduces a computationally efficient ab initio method to study the dynamics of single molecules within collective light-matter states, advancing understanding in polaritonic and QED chemistry.

Contribution

A novel embedding approach that captures collective effects while maintaining full ab initio detail for individual molecules, suitable for complex chemical reactions.

Findings

Demonstrates linear response of molecules in ensembles

Shows nontrivial dependence of reactions on number of emitters

Provides a new framework bridging classical and quantum descriptions

Abstract

The coherent interaction of a large collection of molecules with a common photonic mode results in strong light-matter coupling, a feature that proved highly beneficial for chemistry and termed the research topics polaritonic and QED chemistry. Considering complex microscopic chemical reactions in combination with a macroscopic number of molecules renders existing ab initio approaches inapplicable. In this work, I introduce a simple approach to capture the collective nature while retaining the full ab initio representation of single molecules. By embedding the majority of the molecular ensemble into the dyadic Green tensor, we obtain a computationally cheap and intuitive description of the dynamic of a single molecule in the ensemble - an approach that seems ideal for polaritonic chemistry. The introduced embedding radiation-reaction potential is thoroughly discussed, including prospects, applications and limitations. A first application demonstrates the linear response of single molecules that are part of a larger ensembles of molecules. Then, by virtue of a simple proton-tunneling model, I illustrate that the influence of collective strong coupling on chemical reactions features a nontrivial dependence on the number of emitters. Bridging classical electrodynamics, quantum optical descriptions and the ab initio description of realistic molecules, this work can serve as guiding light for future developments and investigations in the quickly growing fields of QED chemistry and QED material design.