Chemical reactivity under collective vibrational strong coupling
arXiv:2206.08937 · doi:10.1063/5.0124551
Abstract
Recent experiments of chemical reactions in optical cavities have shown great promise to alter and steer chemical reactions but still remain poorly understood theoretically. In particular the origin of resonant effects between the cavity and certain vibrational modes in the collective limit is still subject to active research. In this paper, we study unimolecular dissociation reactions of many molecules collectively interacting with an infrared cavity mode through their vibrational dipole moment. We find that the reaction rate can slow down by increasing the number of aligned molecules if the cavity mode is resonant with a vibrational frequency of the molecules. We also discover a simple scaling relation that scales with the collective Rabi splitting to estimate the onset of reaction rate modification by collective vibrational strong coupling and numerically demonstrate these effects for up to 10,000 molecules.
arXiv comment8 pages, 9 figures
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Cited by in corpus (14)
- Shining Light on the Microscopic Resonant Mechanism Responsible for Cavity-Mediated Chemical Reactivity
- Quantum Dynamics of Vibrational Polariton Chemistry
- Swinging between shine and shadow: Theoretical advances on thermally-activated vibropolaritonic chemistry (a perspective)
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- Investigating the Collective Nature of Cavity Modified Chemical Kinetics under Vibrational Strong Coupling
- Vibrational polariton transport in disordered media
- Dissociation dynamics of a diatomic molecule in an optical cavity
- Vibropolaritonic Reaction Rates in the Collective Strong Coupling Regime: Pollak-Grabert-Hänggi Theory
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- Multimode vibrational coupling across the insulator-to-metal transition in 1T-TaS in THz cavities