Cavity Field-Driven Symmetry Breaking and Modulation of Vibrational Properties: Insights from the Analytical QED-HF Hessian

Abstract

In this work, we present the analytical derivation and implementation of the quantum electrodynamics Hartree-Fock Hessian. We investigate how electronic strong coupling influences molecular vibrational properties, applying this framework to formaldehyde, p-nitroaniline, and adamantane. Our analysis reveals cavity-induced changes in vibrational frequencies and intensities. Additionally, we show how the quantum electromagnetic field breaks molecular symmetry, activating previously forbidden infrared transitions. Our findings highlight the potential of strong coupling as a method for controlling and modulating molecular vibrational properties.