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Theoretical study of kinetics of proton coupled electron transfer in photocatalysis

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.