Quantum Effects in Chemical Reactions under Polaritonic Vibrational Strong Coupling
Name
2109.13690.pdf
Description
Accepted version
Size
2.7 MB
Format
Unknown
Checksum (MD5)
65ac7f30a8df2515fff23a91a2a858d8
Author(s)
Yang, Pei-Yun
Cao, Jianshu
Date Issued
September 2021
Journal
Journal of Physical Chemistry Letters
Publisher
American Chemical Society (ACS)
Citation
Yang, Pei-Yun and Cao, Jianshu. 2021. "Quantum Effects in Chemical Reactions under Polaritonic Vibrational Strong Coupling." Journal of Physical Chemistry Letters, 12 (39).
Version
Author's final manuscript
Abstract
The electromagnetic field in an optical cavity can dramatically modify and even control chemical reactivity via vibrational strong coupling (VSC). Since the typical vibration and cavity frequencies are considerably larger than thermal energy, it is essential to adopt a quantum description of cavity-catalyzed adiabatic chemical reactions. Using quantum transition state theory (TST), we examine the coherent nature of adiabatic reactions in cavities and derive the cavity-induced changes in eigenfrequencies, zero-point energy, and quantum tunneling. The resulting quantum TST calculation allows us to explain and predict the resonance effect (i.e., maximal kinetic modification via tuning the cavity frequency), collective effect (i.e., linear scaling with the molecular density), and selectivity (i.e., cavity-induced control of the branching ratio). The TST calculation is further supported by perturbative analysis of polariton normal modes, which not only provides physical insights to cavity-catalyzed chemical reactions but also presents a general approach to treat other VSC phenomena.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
Terms of Use
Creative Commons Attribution-Noncommercial-Share Alike
Persistent DSpace Link
DOI of Published Version
https://doi.org/10.1021/acs.jpclett.1c02210
