Photocatalysis induced by sunlight is one of the most promising approaches to environmental protection, solar energy conversion, and sustainable production of fuels. The computational modeling of photocatalysis is a rapidly expanding field that requires to adapt and to further develop the available theoretical tools. The coupled transfer of protons and electrons is an important reaction during photocatalysis. In this work, we present the first step of our methodology development in which we apply the existing kinetic theory of such coupled transfer to a model system, namely, methanol photodissociation on the rutile TiO₂(110) surface, with the help of high-level first-principles calculations. Moreover, we adapt the Stuchebrukhov–Hammes-Schiffer kinetic theory, where we use the Georgievskii–Stuchebrukhova vibronic coupling to calculate the rate constant of the proton coupled electron transfer reaction for a particular pathway. In particular, we propose a modified expression to calculate the rate constant, which enforces the near-resonance condition for the vibrational wave function during proton tunneling.

中文翻译：

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光催化中质子耦合电子转移动力学的理论研究

阳光引起的光催化作用是实现环境保护，太阳能转换和燃料可持续生产的最有前途的方法之一。光催化的计算模型是一个快速扩展的领域，需要适应并进一步发展可用的理论工具。质子和电子的耦合转移是光催化过程中的重要反应。在这项工作中，我们介绍了方法论发展的第一步，其中我们将这种耦合转移的现有动力学理论应用于模型系统，即金红石型TiO ₂上的甲醇光解离（110）表面，借助高级第一性原理计算。此外，我们采用了Stuchebrukhov–Hammes-Schiffer动力学理论，其中我们使用Georgievskii–Stuchebrukhova振动耦合来计算特定路径下质子耦合电子转移反应的速率常数。特别是，我们提出了一个修正的表达式来计算速率常数，该常数对质子隧穿过程中的振动波函数施加了近共振条件。