Selective Excitation of IR-Inactive Modes via Vibrational Polaritons: Insights from Atomistic Simulations (2501.09094v2)

Abstract: Vibrational polaritons, hybrid light-matter states formed between molecular vibrations and infrared (IR) cavity modes, provide a novel approach for modifying chemical reaction pathways and energy transfer processes. For vibrational polaritons involving condensed-phase molecules, the short polariton lifetime raises debate over whether pumping polaritons may produce different effects on molecules compared to directly exciting the molecules in free space or under weak coupling. Here, for liquid methane under vibrational strong coupling, classical cavity molecular dynamics simulations show that pumping the upper polariton (UP) formed by the asymmetric bending mode of methane can sometimes selectively excite the IR-inactive symmetric bending mode. This finding is validated when the molecular system is described using both empirical force fields and machine-learning potentials, also in qualitative agreement with analytical theory of polariton energy transfer rates based on Fermi's golden rule calculations. Additionally, our study suggests that polariton-induced energy transfer to IR-inactive modes reaches maximal efficiency when the UP has significant contributions from both photons and molecules, underscoring the importance of light-matter hybridization. As IR-inactive vibrational modes are generally inaccessible to direct IR excitation, our study highlights the unique role of polariton formation in selectively controlling IR-inactive vibrations. Since this polariton-induced process occurs after the polariton decays, it may impact IR photochemistry on a timescale longer than the polariton lifetime, as observed in experiments.