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Cavity frequency-dependent theory for vibrational polariton chemistry
Xinyang Li1, Arkajit Mandal2, Pengfei Huo3,4
1Department of Chemistry, University of Rochester, Rochester, NY, USA.
Nature Communications
|February 27, 2021
Summary
Optical microcavities can alter chemical reactions. This study explains how vibrational strong coupling (VSC) modifies reactivity through non-Markovian cavity dynamics, affecting reaction rates based on photon frequency.
Area of Science:
- Physical Chemistry
- Quantum Optics
- Chemical Physics
Background:
- Experiments show optical microcavities can control chemical reactivity.
- Transition state theory predicts no change in reaction barrier height.
- Polariton chemistry explores molecule-cavity interactions.
Purpose of the Study:
- To provide a theoretical explanation for cavity-induced modification of ground-state reactivity.
- To investigate the role of vibrational strong coupling (VSC) in polariton chemistry.
- To elucidate the mechanism behind photon frequency-dependent reactivity changes.
Main Methods:
- Developed a theoretical framework based on non-Markovian dynamics of the cavity radiation mode.
- Employed an analytical non-Markovian rate theory for a single molecule-cavity system.
- Performed direct numerical calculations of transmission coefficients.
Main Results:
- VSC kinetics modification arises from non-Markovian cavity mode dynamics.
- A dynamical caging effect on the reaction coordinate suppresses reaction rates.
- Suppression occurs for photon frequencies near the barrier frequency.
Conclusions:
- The study provides a theoretical explanation for reactivity control in optical microcavities.
- Non-Markovian cavity dynamics and dynamical caging are key mechanisms.
- Results explain photon frequency-dependent modifications in VSC polariton chemistry.
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