Semiclassical truncated-Wigner-approximation theory of
molecular-vibration-polariton dynamics in optical cavities
- URL: http://arxiv.org/abs/2311.07827v2
- Date: Mon, 22 Jan 2024 04:21:55 GMT
- Title: Semiclassical truncated-Wigner-approximation theory of
molecular-vibration-polariton dynamics in optical cavities
- Authors: Nguyen Thanh Phuc
- Abstract summary: We develop here the semiclassical theory of molecular-vibration-polariton dynamics based on the truncated Wigner approximation (TWA)
The validity of TWA is examined by comparing it with the fully quantum dynamics of a single-molecule system.
The collective and resonance effects of molecular-vibration-polariton formation on the nuclear dynamics are observed in a system of many molecules.
- Score: 0.0
- License: http://creativecommons.org/licenses/by/4.0/
- 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.
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