论文标题
过渡状态理论中的极化正常模式
Polaritonic normal modes in Transition State Theory
论文作者
论文摘要
一系列实验表明,分子和谐振红外光学微神经模式的振动激发之间的强光耦合会导致改进的热激活动力学。但是,Feist和同事[\ Emph {Phys。 Rev. X.},\ textbf {9},021057(2019)]最近证明,在过渡状态理论中,强光结合与反应性模式的效果是静电性的,并且基本上独立于光 - 谐音,甚至独立于振动极性的形成。为了进一步详细分析这种令人困惑的理论结果,我们在新的光线下对其进行了重新访问,从而为过渡态和反应物配置的正常模式分析,用于在腔中任意数量的分子的集合,获得简单的分析表达式,从而产生类似的结论作为FEIST。尽管这些效果在光学微腔中相关,如果分子偶极子是各向异性对齐的,或者在光子模式极端限制的腔中,它们在微腔中的各向同性溶液中它们变得可忽略不计。可以得出结论,需要进一步的研究来跟踪实验观察到的动力学的起源。
A series of experiments demonstrate that strong light-matter coupling between vibrational excitations in isotropic solutions of molecules and resonant infrared optical microcavity modes leads to modified thermally-activated kinetics. However, Feist and coworkers [\emph{Phys. Rev. X.}, \textbf{9}, 021057(2019)] have recently demonstrated that, within transition state theory, the effects of strong light-matter coupling with reactive modes are electrostatic and essentially independent of light-matter resonance or even of the formation of vibrational polaritons. To analyze this puzzling theoretical result in further detail, we revisit it under a new light, invoking a normal mode analysis of the transition state and reactant configurations for an ensemble of an arbitrary number of molecules in a cavity, obtaining simple analytical expressions that produce similar conclusions as Feist. While these effects become relevant in optical microcavities if the molecular dipoles are anisotropically aligned, or in cavities with extreme confinement of the photon modes, they become negligible for isotropic solutions in microcavities. It is concluded that further studies are necessary to track the origin of the experimentally observed kinetics.