Energy-efficient pathway for selectively exciting solute molecules to high vibrational states via solvent vibration-polariton pumping

Abstract

Selectively exciting target molecules to high vibrational states is inefficient in the liquid phase, which restricts the use of IR pumping to catalyze ground-state chemical reactions. Here, we demonstrate that this inefficiency can sometimes be solved by confining the liquid to an optical cavity under vibrational strong coupling conditions. For a liquid solution of 13CO2 solute in a 12CO2 solvent, cavity molecular dynamics simulations show that exciting a polariton (hybrid light-matter state) of the solvent with an intense laser pulse, under suitable resonant conditions, may lead to a very strong (> 3 quanta) and ultrafast (< 1 ps) excitation of the solute, even though the solvent ends up being barely excited. By contrast, outside a cavity the same input pulse fluence can excite the solute by only half a vibrational quantum and the selectivity of excitation is low. Our finding is robust under different cavity volumes, which may lead to observable cavity enhancement on IR photochemical reactions in Fabry-Pérot cavities.

10 pages of manuscript + 23 pages of SI

References in corpus (7)

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• Intermolecular interactions in optical cavities: an ab initio QED study
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Cited by in corpus (12)

• Molecular polaritonics: Chemical Dynamics under strong Light-Matter Coupling
• i-PI 3.0: a flexible and efficient framework for advanced atomistic simulations
• Polariton relaxation under vibrational strong coupling: Comparing cavity molecular dynamics simulations against Fermi's golden rule rate
• Cavity-Altered Thermal Isomerization Rates and Dynamical Resonant Localization in Vibro-Polaritonic Chemistry
• QM/MM Modeling of Vibrational Polariton Induced Energy Transfer and Chemical Dynamics
• Vibrational strong coupling in liquid water from cavity molecular dynamics
• Dissociation dynamics of a diatomic molecule in an optical cavity
• Selective Excitation of IR-Inactive Modes via Vibrational Polaritons: Insights from Atomistic Simulations
• Control and enhancement of single-molecule electroluminescence through strong light-matter coupling
• Understanding polaritonic chemistry from ab initio quantum electrodynamics
• On-the-Fly Cavity-Molecular Dynamics of Vibrational Polaritons
• Linear and nonlinear vibrational excitation driven by molecular polaritons