Engineering molecular potential energy surfaces using magnetic cavity quantum electrodynamics

TL;DR

This paper explores how magnetic cavity quantum electrodynamics can modify molecular potential energy surfaces, affecting stability, electronic states, and aromaticity, with potential applications in cavity-controlled chemistry.

Contribution

It introduces a high-precision quantum Monte Carlo approach to study cavity-molecule interactions, revealing novel effects on molecular stability and electronic structure.

Findings

Strong cavity coupling makes H2's ground state metastable and inverts the singlet-triplet gap.

Magnetic cavities stabilize symmetric geometries in ring molecules, preventing Jahn-Teller distortions.

Cavity effects are amplified with increased molecule concentration, enabling cavity-altered chemistry.

Abstract

We investigate the effects of coupling a quantum-magnetic cavity field to molecules. Our high-precision auxiliary-field quantum Monte Carlo calculations capture the effect of the cavity field in the presence of electron correlations, and their interplay and competition. In H$_2$, we find that a strong enough cavity coupling makes the original bound ground state metastable, along with inverting the singlet-triplet gap. In ring molecules (e.g., H$_n$), the magnetic cavity coupling stabilizes symmetric geometries. As a consequence, open-shell rings such as H$_4$, H$_8$, or C$_4$H$_4$, which would undergo Jahn-Teller distortions outside of the cavity, obtain exotic spin or ring-current polarized, antiaromatic ground states. These effects are enhanced by increasing the molecule concentration inside the cavity. Our results suggest cavity quantum electrodynamics beyond the long-wavelength approximation as a promising avenue for cavity-altered chemistry.