Mandal Arkajit, Li Xinyang, Huo Pengfei
Department of Chemistry, University of Rochester, Rochester, New York 14627, USA.
J Chem Phys. 2022 Jan 7;156(1):014101. doi: 10.1063/5.0074106.
We theoretically demonstrate that the chemical reaction rate constant can be significantly suppressed by coupling molecular vibrations with an optical cavity, exhibiting both the collective coupling effect and the cavity frequency modification of the rate constant. When a reaction coordinate is strongly coupled to the solvent molecules, the reaction rate constant is reduced due to the dynamical caging effect. We demonstrate that collectively coupling the solvent to the cavity can further enhance this dynamical caging effect, leading to additional suppression of the chemical kinetics. This effect is further amplified when cavity loss is considered.
我们从理论上证明，通过将分子振动与光学腔耦合，可以显著抑制化学反应速率常数，这既表现出集体耦合效应，又体现了速率常数的腔频率修正。当反应坐标与溶剂分子强烈耦合时，由于动态笼效应，反应速率常数会降低。我们证明，将溶剂与腔集体耦合可以进一步增强这种动态笼效应，从而导致对化学动力学的额外抑制。当考虑腔损耗时，这种效应会进一步放大。
