Intermolecular interactions in optical cavities: An ab initio QED study.

Tor S Haugland,Henrik Koch,Christian Schäfer,Angel Rubio,Enrico Ronca

doi:10.1063/5.0039256

Abstract

Intermolecular bonds are weak compared to covalent bonds, but they are strong enough to influence the properties of large molecular systems. In this work, we investigate how strong light-matter coupling inside an optical cavity can modify intermolecular forces and illustrate the varying necessity of correlation in their description. The electromagnetic field inside the cavity can modulate the ground state properties of weakly bound complexes. Tuning the field polarization and cavity frequency, the interactions can be stabilized or destabilized, and electron densities, dipole moments, and polarizabilities can be altered. We demonstrate that electron-photon correlation is fundamental to describe intermolecular interactions in strong light-matter coupling. This work proposes optical cavities as a novel tool to manipulate and control ground state properties, solvent effects, and intermolecular interactions for molecules and materials.

Highlights

Intermolecular interactions play a fundamental role in chemistry and physics, and are especially important in describing the properties of large systems
We investigate how strong light-matter coupling inside an optical cavity can modify these intermolecular forces
Intermolecular energies are substantially weaker (1-300 meV) and they arise from van der Waals interaction or electrostatics.[55]

Summary

Introduction

Intermolecular interactions play a fundamental role in chemistry and physics, and are especially important in describing the properties of large systems They contribute to solvation processes,[1] interactions in liquids,[2] gas phase reactivity,[3] formation of higher order structures in biological macromolecules,[4] and multi-layer 2D materials.[5,6,7,8] The ability to induce even minor modifications in the intermolecular forces can have large impact on the macroscopic properties of molecular systems. Cavities have been applied to: enhance charge and energy transfer,[21,22,23,24,25,26,27] design materials,[28] and control superconductivity.[29,30,31] These applications highlight the use of confined light in chemistry

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