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Resonance Theory of Vibrational Strong Couplings in Polariton Chemistry

preprint
submitted on 03.09.2020, 20:23 and posted on 04.09.2020, 11:08 by Xinyang Li, Arkajit Mandal, Pengfei Huo
In this work, we present a new theoretical explanation of the resonance vibrational strong coupling (VSC) regime in polariton chemistry. Coupling molecular vibrations and the cavity photonic excitation has experimentally demonstrated to strongly influence the ground state kinetics of a chemical reaction. Our theoretical results suggest that the VSC kinetics modification originates from the non-Markovian behavior of the cavity radiation mode when coupling to the molecule, leading to the dynamical caging of the reaction coordinate and the suppression of chemical reaction rate for a given range of photon frequency that is close to the barrier frequency. Further, we use a simple analytical non-Markovian rate theory to describe a single molecular system coupled to a radiation mode in an optical cavity. We demonstrate the accuracy of the rate theory by performing a numerical calculation in a one-dimensional model molecular system coupled to the cavity. Our simulations and analytical theory demonstrate the importance of dynamical effects in VSC polaritonic chemistry.

Funding

National Science Foundation CAREER Award under Grant No. CHE-1845747

National Science Foundation "Enabling Quantum Leap in Chemistry'' program under a Grant number CHE-1836546

Cottrell Scholar award (a program by of Research Corporation for Science Advancement)

History

Email Address of Submitting Author

pengfei.huo@rochester.edu

Institution

University of Rochester

Country

United States

ORCID For Submitting Author

0000-0002-8639-9299

Declaration of Conflict of Interest

no conflict of interest

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