Cavity-Born-Oppenheimer Hartree-Fock Ansatz: Light-matter Properties of Strongly Coupled Molecular Ensembles

TL;DR

This paper introduces a novel ab-initio Hartree-Fock approach within the cavity Born-Oppenheimer approximation to accurately model and analyze the collective light-matter interactions in strongly coupled molecular ensembles, emphasizing cavity-mediated inter-molecular effects.

Contribution

The paper develops a non-perturbative, self-consistent Hartree-Fock ansatz that incorporates cavity-mediated dipole self-energy for ensembles, advancing theoretical understanding of polaritonic chemistry.

Findings

Cavity-mediated inter-molecular dipole-dipole interactions significantly alter molecular energies.

The approach captures collective effects in strongly coupled hydrogen fluoride molecules.

Results demonstrate the importance of cavity effects in molecular ensemble behavior.

Abstract

Experimental studies indicate that optical cavities can affect chemical reactions, through either vibrational or electronic strong coupling and the quantized cavity modes. However, the current understanding of the interplay between molecules and confined light modes is incomplete. Accurate theoretical models, that take into account inter-molecular interactions to describe ensembles, are therefore essential to understand the mechanisms governing polaritonic chemistry. We present an ab-initio Hartree-Fock ansatz in the framework of the cavity Born-Oppenheimer approximation and study molecules strongly interacting with an optical cavity. This ansatz provides a non-perturbative, self-consistent description of strongly coupled molecular ensembles taking into account the cavity-mediated dipole self-energy contributions. To demonstrate the capability of the cavity Born-Oppenheimer Hartree-Fock ansatz, we study the collective effects in ensembles of strongly coupled diatomic hydrogen fluoride molecules. Our results highlight the importance of the cavity-mediated inter-molecular dipole-dipole interactions, which lead to energetic changes of individual molecules in the coupled ensemble.