Molecular van der Waals fluids in cavity quantum electrodynamics

TL;DR

This paper demonstrates how strong light-matter coupling in cavity quantum electrodynamics can be used to manipulate van der Waals interactions, affecting the structural and thermodynamic properties of molecular fluids, with potential applications in controlling molecular systems.

Contribution

It introduces a novel approach to tune van der Waals interactions using cavity quantum electrodynamics and develops machine learning-based potentials for large molecular systems.

Findings

Van der Waals interactions can be modulated by cavity coupling.

Strong light-matter coupling influences molecular orientation and order.

Simulations show control over thermodynamic properties of molecular fluids.

Abstract

Intermolecular van der Waals interactions are central to chemical and physical phenomena ranging from biomolecule binding to soft-matter phase transitions. However, there are currently very limited approaches to manipulate van der Waals interactions. In this work, we demonstrate that strong light-matter coupling can be used to tune van der Waals interactions, and, thus, control the thermodynamic properties of many-molecule systems. Our analyses reveal orientation dependent single molecule energies and interaction energies for van der Waals molecules (for example, H$_{2}$). For example, we find intermolecular interactions that depend on the distance between the molecules $R$ as $R^{-3}$ and $R^{0}$. Moreover, we employ non-perturbative \textit{ab initio} cavity quantum electrodynamics calculations to develop machine learning-based interaction potentials for molecules inside optical cavities. By simulating systems ranging from $12$ H$_2$ to $144$ H$_2$ molecules, we demonstrate that strong light-matter coupling can tune the structural and thermodynamic properties of molecular fluids. In particular, we observe varying degrees of orientational order as a consequence of cavity-modified interactions, and we explain how quantum nuclear effects, light-matter coupling strengths, number of cavity modes, molecular anisotropies, and system size all impact the extent of orientational order. These simulations and analyses demonstrate both local and collective effects induced by strong light-matter coupling and open new paths for controlling the properties of molecular clusters.