Resonance Enhancement of Vibrational Polariton Chemistry Obtained from the Mixed Quantum-Classical Dynamics Simulations

We applied a variety of mixed quantum-classical (MQC) approaches to simulate the VSC-influenced reaction rate constant. All of these MQC simulations treat the key vibrational levels associated with the reaction coordinate in the quantum subsystem (as quantum states), whereas all other degrees of freedom (DOFs) are treated inside the classical subsystem. We find that as long as we have the quantum state descriptions for the vibrational DOFs, one can correctly describe the VSC resonance condition when the cavity frequency matches the bond vibrational frequency. This correct resonance behavior can be obtained regardless of the detailed MQC methods one uses. The results suggest that the MQC approaches can generate semi-quantitative agreement with the exact results for rate constant changes when changing the cavity frequency, the light-matter coupling strength, or the cavity lifetime. The finding of this work suggests that one can use computationally economic MQC approaches to explore the collective coupling scenario when many molecules are collectively coupled to many cavity modes in the future.