论文标题
光催化中质子耦合电子转移动力学的理论研究
Theoretical study of kinetics of proton coupled electron transfer in photocatalysis
论文作者
论文摘要
阳光引起的光催化是环境保护，太阳能转化和燃料可持续生产的最有希望的方法之一。光催化的计算建模是一个快速消耗的领域，需要适应并进一步开发可用的理论工具。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，我们介绍了方法论开发的第一步，在该方法中，我们将这种耦合转移的现有动力学理论应用于模型系统，即在金红石Tio $ _2 $ _2 $（110）表面上的甲醇照相分解，并借助高级第一原则计算。此外，我们适应了Stuchebrukhov-Hammes-Schiffer动力学理论，在那里我们使用Georgievskii-Stuchebrukhova振动耦合来计算特定途径的质子耦合电子传递反应的速率常数。特别是，我们提出了一个修改的表达式，以计算质子隧穿中振动波函数的近谐度条件的速率常数。
Photocatalysis induced by sunlight is one of the most promising approach to environmental protection, solar energy conversion and sustainable production of fuels. The computational modeling of photocatalysis is a rapidly expending field which requires to adapt and further develop the available theoretical tools. The coupled transfer of proton and electron is an important reaction during photocatalysis. In this work, we present the first step of our methodology development in which we apply existing kinetic theory of such coupled transfer to a model system, namely, methanol photo-dissociation on rutile TiO$_2$(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 wavefunction during proton tunneling.
