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Under vibrational strong coupling (VSC), the formation of molecularpolaritons may significantly modify the photo-induced or thermal properties ofmolecules. In an effort to understand these intriguing modifications, bothexperimental and theoretical studies have focused on the ultrafast dynamics ofvibrational polaritons. Here, following our recent work [J. Chem. Phys., 154,094124, (2021)], we systematically study the mechanism of polariton relaxationfor liquid CO2 under a weak external pumping. Classical cavity moleculardynamics (CavMD) simulations show that polariton relaxation results from thecombined effects of (i) cavity loss through the photonic component and (ii)dephasing of the bright-mode component to vibrational dark modes as mediated byintermolecular interactions. The latter polaritonic dephasing rate isproportional to the product of the weight of the bright mode in the polaritonwave function and the spectral overlap between the polariton and dark modes.Both these factors are sensitive to parameters such as the Rabi splitting andcavity mode detuning. Compared to a Fermi's golden rule calculation based on atight-binding harmonic model, CavMD yields a similar parameter dependence forthe upper polariton relaxation lifetime but sometimes a modest disagreement forthe lower polariton. We suggest that this disagreement results frompolariton-enhanced molecular nonlinear absorption due to molecularanharmonicity, which is not included in our analytical model. We also summarizerecent progress on probing nonreactive VSC dynamics with CavMD.

Polariton relaxation under vibrational strong coupling: Comparing cavity molecular dynamics simulations against Fermi's golden rule rate