Non-equilibrium origin of cavity-induced resonant modifications of chemical reactivities

Abstract: In this work, we investigate the influence of light-matter coupling on reaction dynamics and equilibrium properties of a single molecule inside an optical cavity. The reactive molecule is modeled using a triple-well potential, allowing two competing reaction pathways that yield distinct products. Dynamical and equilibrium simulations are performed using the numerically exact hierarchical equations of motion approach in real- and imaginary-time formulations, respectively, both implemented with tree tensor network decomposition schemes. We consider two illustrative cases: one dominated by slow kinetics and another by ultrafast processes. Our results demonstrate that in both scenarios, the rates of ground-state reaction pathways can be selectively enhanced when the cavity frequency is tuned in resonance with the relevant vibrational transition, which directly leads to the formation of the corresponding product. In addition, due to the anharmonicity of chemical reactions, cavity-induced vibrational transitions within the reactant region can also influence reaction rates even when they do not directly result in product formation. However, we found that the equilibrium populations remain unchanged when the molecule is moved into the cavity, regardless of the cavity frequency. Thus, our proof-of-concept study highlights that cavity-induced modifications of chemical reactivities in resonant conditions arise from dynamical and non-equilibrium interactions between the cavity mode and molecular vibrations, rather than from the significant changes in equilibrium properties.