论文标题
部分可观测时空混沌系统的无模型预测
Quantum Dynamics of Vibrational Polariton Chemistry
论文作者
论文摘要
我们采用精确的量子机械模拟技术来研究凝结相中腔体修饰化学反应的模型。该模型包含反应坐标与通用溶剂的耦合，腔耦合与反应坐标或非反应性模式以及腔与有损模式的耦合。因此，包括化学反应的腔体修饰所需的许多最重要的特征。我们发现，当分子耦合到光学腔时，必须机械处理问题量子以获取反应性改变的定量说明。我们发现与量子机械状态分裂和共振相关的速率常数的巨大变化。与以前的计算相比，从我们的模拟中出现的特征更接近实验中观察到的特征，即使实际上耦合和空腔损失的值也很小。这项工作强调了对振动极化化学的完全量子处理的重要性。
We employ an exact quantum mechanical simulation technique to investigate a model of cavity-modified chemical reactions in the condensed phase. The model contains the coupling of the reaction coordinate to a generic solvent, cavity coupling to either the reaction coordinate or a non-reactive mode, and the coupling of the cavity to lossy modes. Thus, many of the most important features needed for realistic modeling of the cavity modification of chemical reactions are included. We find that when a molecule is coupled to an optical cavity it is essential to treat the problem quantum mechanically in order to obtain a quantitative account of alterations to reactivity. We find sizable and sharp changes in the rate constant that are associated with quantum mechanical state splittings and resonances. The features that emerge from our simulations are closer to those observed in experiments than are previous calculations, even for realistically small values of coupling and cavity loss. This work highlights the importance of a fully quantum treatment of vibrational polariton chemistry.
