Quantum Effects in Chemical Reactions under Polaritonic Vibrational Strong Coupling

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 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.

References in corpus (6)

• Cavity-controlled chemistry in molecular ensembles
• Atoms and Molecules in Cavities: From Weak to Strong Coupling in QED Chemistry
• Cavity Casimir-Polder forces and their effects in ground state chemical reactivity
• Many-molecule reaction triggered by a single photon in polaritonic chemistry
• Shining Light on the Microscopic Resonant Mechanism Responsible for Cavity-Mediated Chemical Reactivity
• An exact equilibrium reduced density matrix formulation I: The influence of noise, disorder, and temperature on localization in excitonic systems