Semiclassical truncated-Wigner-approximation theory of molecular-vibration-polariton dynamics in optical cavities

Abstract: It has been experimentally demonstrated that molecular-vibration polaritons formed by strong coupling of a molecular vibration to an infrared cavity mode can significantly modify the physical properties and chemical reactivity of various molecular systems. However, a complete theoretical understanding of the underlying mechanisms of the modifications remains elusive due to the complexity of the hybrid system, especially the collective nature of polaritonic states in systems containing many molecules. We develop here the semiclassical theory of molecular-vibration-polariton dynamics based on the truncated Wigner approximation (TWA) that is tractable in large molecular systems and simultaneously captures the quantum character of photons in the optical cavity. The theory is then applied to investigate the nuclear quantum dynamics of a system of identical diatomic molecules having the ground-state Morse potential and strongly coupled to an infrared cavity mode in the ultrastrong coupling regime. The validity of TWA is examined by comparing it with the fully quantum dynamics of a single-molecule system for two different initial states in the dipole and Coulomb gauges. For the initial tensor-product ground state in the dipole gauge, which corresponds to a light-matter entangled state in the Coulomb gauge, the collective and resonance effects of molecular-vibration-polariton formation on the nuclear dynamics are observed in a system of many molecules.