The standard description of cavity-modified molecular reactions typically involves a single (resonant) mode, while in reality, the quantum cavity supports a range of photon modes. Here, we demonstrate that as more photon modes are accounted for, physicochemical phenomena can dramatically change, as illustrated by the cavity-induced suppression of the important and ubiquitous process of proton-coupled electron-transfer. Using a multi-trajectory Ehrenfest treatment for the photon-modes, we find that self-polarization effects become essential, and we introduce the concept of self-polarization-modified Born–Oppenheimer surfaces as a new construct to analyze dynamics. As the number of cavity photon modes increases, the increasing deviation of these surfaces from the cavity-free Born–Oppenheimer surfaces, together with the interplay between photon emission and absorption inside the widening bands of these surfaces, leads to enhanced suppression. The present findings are general and will have implications for the description and control of cavity-driven physical processes of molecules, nanostructures, and solids embedded in cavities.

中文翻译：

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腔内多种模式对自极化和光化学抑制的影响。

腔修饰分子反应的标准描述通常涉及单个（共振）模式，而实际上，量子腔支持一系列光子模式。在这里，我们证明，随着更多的光子模式被考虑，理化现象会发生巨大变化，如空腔诱导的重要且普遍存在的质子耦合电子转移过程所说明的那样。通过对光子模式使用多轨迹Ehrenfest处理，我们发现自极化效应变得至关重要，并且我们引入了自极化修饰的Born–Oppenheimer表面的概念，作为分析动力学的新结构。随着腔体光子模数的增加，这些表面与无腔体的Born–Oppenheimer表面的偏差越来越大，这些表面的加宽带内的光子发射与吸收之间的相互作用，导致抑制作用增强。目前的发现是一般性的，将对描述和控制腔驱动的分子，纳米结构和嵌入腔中的固体的物理过程产生影响。