Quantum Effects in Chemical Reactions under Polaritonic Vibrational Strong Coupling

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 cavityinduced 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.

Automated summary

The electromagnetic field in an optical cavity can modify and control chemical reactions through vibrational strong coupling, requiring a quantum description. The use of quantum transition state theory helps to explain resonant effect, collective effect, and selectivity in cavity-catalyzed reactions. Perturbative analysis of polariton normal modes supports the theoretical calculations and provides a general approach for other VSC phenomena.