2021/09/28 by Pei-Yun Yang, Yang, Peiyun, Jianshu Cao +1 · 6 citations
Engineering · Physics and Astronomy · #Chemical Physics (physics.chem-ph) #FOS: Physical sciences #Quantum Physics (quant-ph) #Quantum and electron transport phenomena #Strong Light-Matter Interactions #Thermal Radiation and Cooling Technologies
paper · pdf · doi:10.48550/arxiv.2109.13690
openalex publication_date 2021/09/28 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/28
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 higher 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 and derive the cavity-induced changes in eigen frequencies, 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.