Ab Initio Linear-Response Approach to Vibro-Polaritons in the Cavity Born–Oppenheimer Approximation

[Image: see text] Recent years have seen significant developments in the study of strong light–matter coupling including the control of chemical reactions by altering the vibrational normal modes of molecules. In the vibrational strong coupling regime, the normal modes of the system become hybrid modes which mix nuclear, electronic, and photonic degrees of freedom. First-principles methods capable of treating light and matter degrees of freedom on the same level of theory are an important tool in understanding such systems. In this work, we develop and apply a generalized force constant matrix approach to the study of mixed vibration-photon (vibro-polariton) states of molecules based on the cavity Born–Oppenheimer approximation and quantum-electrodynamical density-functional theory. With this method, vibro-polariton modes and infrared spectra can be computed via linear-response techniques analogous to those widely used for conventional vibrations and phonons. We also develop an accurate model that highlights the consistent treatment of cavity-coupled electrons in the vibrational strong coupling regime. These electronic effects appear as new terms previously disregarded by simpler models. This effective model also allows for an accurate extrapolation of single and two molecule calculations to the collective strong coupling limit of hundreds of molecules. We benchmark these approaches for single and many CO(2) molecules coupled to a single photon mode and the iron pentacarbonyl Fe(CO)(5) molecule coupled to a few photon modes. Our results are the first ab initio results for collective vibrational strong coupling effects. This framework for efficient computations of vibro-polaritons paves the way to a systematic description and improved understanding of the behavior of chemical systems in vibrational strong coupling.