Understanding the cavity Born-Oppenheimer approximation.

Abstract

Experiments have demonstrated that vibrational strong coupling between molecular vibrations and light modes can significantly change molecular properties, such as ground-state reactivity. Theoretical studies toward the origin of this exciting observation can roughly be divided into two categories, with studies based on Hamiltonians that simply couple a molecule to a cavity mode via its ground-state dipole moment on the one hand, and on the other hand ab initio calculations that self-consistently include the effect of the cavity mode on the electronic ground state within the cavity Born-Oppenheimer (CBO) approximation; these approaches are not equivalent. The CBO approach is more rigorous, but unfortunately it requires the rewriting of electronic-structure code, and its results may sometimes be hard to physically interpret. In this work, we exploit the relation between the two approaches and demonstrate on a real molecule (hydrogen fluoride) that for realistic coupling strengths, we can recover CBO energies and spectra to high accuracy using only out-of-cavity quantities from standard electronic-structure calculations. In doing so, we discover what thephysical effects underlying the CBO results are. Our methodology can aid in incorporating more possibly important features in models, play a pivotal role in demystifying CBO results, and provide a practical and efficient alternative to full CBO calculations.