论文标题
关于地面真空场催化的起源：平衡考虑
On the Origin of Ground-State Vacuum-Field Catalysis: Equilibrium Consideration
论文作者
论文摘要
最近的实验表明，即使没有外部抽水，振动强耦合（VSC）也可能会显着改变地面化学反应及其速率。这种“真空场催化”的固有机制在很大程度上仍然不清楚。通常，地面电子状态中热反应的修改可能是由平衡或非平衡效应引起的。前者与化学反应速率的过渡状态理论所表达的反应物平衡分布的修改有关，而后者源于触及和离开过渡构型的动力学。在这里，我们检查了通过过渡状态理论计算的腔环境中对化学速率的VSC效应。我们的方法是检查耦合到腔模式的影响（S）对与反应坐标相关的平均力（PMF）潜力的影响。在经典核和经典光子的背景下，我们发现，尽管PMF可能受空腔环境的影响，但对于用于检查VSC情况的通常腔体而言，这种效果可以忽略不计。
Recent experiments suggest that vibrational strong coupling (VSC) may significantly modify ground-state chemical reactions and their rates even without external pumping. The intrinsic mechanism of this "vacuum-field catalysis" remains largely unclear. Generally, modifications of thermal reactions in the ground electronic states can be caused by equilibrium or non-equilibrium effects. The former are associated with modifications of the reactant equilibrium distribution as expressed by the transition state theory of chemical reaction rates, while the latter stem from the dynamics of reaching and leaving transition configurations. Here, we examine the VSC effect in a cavity environment on chemical rates as calculated by transition state theory. Our approach is to examine the effect of coupling to cavity mode(s) on the potential of mean force (PMF) associated with the reaction coordinate. Within the context of classical nuclei and classical photons, we find that while the PMF can be affected by the cavity environment, this effect is negligible for the usual cavities used to examine VSC situations.
