Strong coupling between localized surface plasmons and molecules by coupled cluster theory

TL;DR

This paper introduces a non-perturbative computational method combining quantum chemistry and plasmonic modeling to study strong light-matter interactions in nanocavities, revealing new effects of plasmon-molecule correlations.

Contribution

It develops a high-level coupled cluster approach to simulate molecular polaritons in plasmonic nanocavities, including effects previously neglected.

Findings

Mutual polarization and correlation effects are significant.

Molecular charge density can be manipulated by nanocavities.

Provides benchmarks for molecular polaritonics methods.

Abstract

Plasmonic nanocavities enable the confinement of molecules and electromagnetic fields within nano-metric volumes. As a consequence, the molecules experience a remarkably strong interaction with the electromagnetic field, to such an extent that the quantum states of the system become hybrids between light and matter: polaritons. Here we present a non-perturbative method to simulate the emerging properties of such polaritons: it combines a high-level quantum chemical description of the molecule with a quantized description of the localized surface plasmons in the nanocavity. We apply the method to molecules of realistic complexity in a typical plasmonic nanocavity, featuring also a subnanometric asperity (picocavity). Our results disclose the effects of the mutual polarization and correlation of plasmons and molecular excitations, disregarded so far. They also quantify to what extent the molecular charge density can be manipulated by nanocavities, and stand as benchmarks to guide the development of methods for molecular polaritonics.