Theoretical study of kinetics of proton coupled electron transfer inphotocatalysis

Photocatalysis induced by sunlight is one of the most promising approaches toenvironmental protection, solar energy conversion, and sustainable production of fuels.The computational modeling of photocatalysis is a rapidly expanding field that requires toadapt and to further develop the available the...

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Bibliographic Details
Published in:The Journal of chemical physics 2020-03, Vol.152 (12)
Main Authors: Yvelin, Giret, Guo Pu, Li-Feng, Wang, Cheng, Jun
Format: Article
Language:English
Subjects:
Electron transfer
Photocatalysis
Physics
Protons
Reaction kinetics
Solar energy conversion
Titanium dioxide
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Summary:Photocatalysis induced by sunlight is one of the most promising approaches toenvironmental protection, solar energy conversion, and sustainable production of fuels.The computational modeling of photocatalysis is a rapidly expanding field that requires toadapt and to further develop the available theoretical tools. The coupled transfer ofprotons and electrons is an important reaction during photocatalysis. In this work, wepresent the first step of our methodology development in which we apply the existingkinetic theory of such coupled transfer to a model system, namely, methanolphotodissociation on the rutile TiO2(110) surface, with the help of high-levelfirst-principles calculations. Moreover, we adapt the Stuchebrukhov–Hammes-Schifferkinetic theory, where we use the Georgievskii–Stuchebrukhova vibronic coupling tocalculate the rate constant of the proton coupled electron transfer reaction for aparticular pathway. In particular, we propose a modified expression to calculate the rateconstant, which enforces the near-resonance condition for the vibrational wave functionduring proton tunneling.
ISSN:0021-9606
1089-7690
DOI:10.1063/5.0001825