Quantum Effects in Chemical Reactions under Polaritonic Vibrational Strong Coupling
| Autor: | Jianshu Cao, Pei-Yun Yang |
|---|---|
| Rok vydání: | 2021 |
| Předmět: |
Electromagnetic field
Physics 010405 organic chemistry Physics::Optics 7. Clean energy 01 natural sciences Molecular physics 0104 chemical sciences law.invention Transition state theory Normal mode law Optical cavity 0103 physical sciences Polariton General Materials Science Physical and Theoretical Chemistry 010306 general physics Adiabatic process Quantum Quantum tunnelling |
| Zdroj: | The journal of physical chemistry letters. 12(39) |
| ISSN: | 1948-7185 |
| Popis: | 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. |
| Databáze: | OpenAIRE |
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