In this manuscript, we provide a general theory for how surface phonons couple to molecular adsorbates. Our theory maps the extended dynamics of a surface’s atomic vibrational motions to a generalized Langevin equation, and by doing so captures these dynamics in a single quantity: the non-Markovian friction. The different frequency components of this friction are the phonon modes of the surface slab weighted by their coupling to the adsorbate degrees of freedom. Using this formalism, we demonstrate that physisorbed species couple primarily to acoustic phonons while chemisorbed species couple to dispersionless local vibrations. We subsequently derive equations for phonon-adjusted reaction rates using transition state theory and demonstrate that these corrections improve agreement with experimental results for CO desorption rates from Pt(111).

中文翻译：

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分子吸附物的声子诱导摩擦理论


在这份手稿中，我们提供了表面声子如何与分子吸附物耦合的一般理论。我们的理论将表面原子振动运动的扩展动力学映射到广义朗之万方程，并通过这样做以单个量捕获这些动力学：非马尔可夫摩擦。该摩擦力的不同频率分量是表面板的声子模式，其通过与吸附物自由度的耦合而加权。使用这种形式，我们证明了物理吸附物质主要与声声子耦合，而化学吸附物质与无色散局部振动耦合。随后，我们使用过渡态理论推导了声子调节反应速率的方程，并证明这些修正提高了与 Pt(111) CO 解吸速率实验结果的一致性。