文献类型：期刊文献

英文题名：Stretching vibration driven adiabatic transfer kinetics for photoexcited hole transfer from semiconductor to adsorbate

作者：Zhou, Min[1];Chen, Dingming[1];Liu, Ying[1];Wang, Haifeng[1]

机构：[1]East China Univ Sci & Technol, Ctr Computat Chem, State Key Lab Green Chem Engn & Ind Catalysis, Shanghai 200237, Peoples R China; East China Univ Sci & Technol, Res Inst Ind Catalysis, Shanghai 200237, Peoples R China

年份：2024

卷号：15

期号：1

外文期刊名：NATURE COMMUNICATIONS

收录：;WOS:【SCI-EXPANDED(收录号:WOS:001335963600026)】；

基金：This project was supported by National Key Research and Development Program of China (2021YFA1500700), NSFC (22202069, 21873028), Special Support by the China Postdoctoral Science Foundation (in front of the website) (2022TQ0106), the China Postdoctoral Science Foundation Funded Project (2022M721141), and the Fundamental Research Funds for the Central Universities.

语种：英文

摘要：Interfacial hole transfer from a photoexcited semiconductor to surface adsorbates is pivotal for initiating solar-to-chemical energy conversion, yet the atomic-level transfer kinetics remains elusive. Using the methoxy/TiO2(110) system as an archetype, here we elucidate the hole transfer mechanism from hole-trapping lattice oxygen to the methoxy adsorbate at gas/solid and liquid/solid interfaces through molecular dynamics simulations and static minimum energy path calculations. Instead of direct nonadiabatic hopping, we uncover an adiabatic migration pathway adapted to local substrate relaxation, driven by a bond-stretching mechanism supported by stronger Ti-O stretching vibrations. Notably, this mechanism persists at the aqueous methoxy/TiO2(110) interface, albeit hindered by interfacial water and coadsorbates. Surprisingly, the hole transfer barriers across various photoexcited adsorbate/TiO2 interfaces correlate more closely with the vertical excitation energies of the adsorbates rather than their redox potentials, indicating an early-type transition-state nature. These insights deepen our understanding of elementary hole transfer kinetics in surface photochemistry. Interfacial hole transfer from photoexcited semiconductors to substrates is an important step in methoxy oxidation on rutile surfaces. Here, using theoretical simulations, the authors show this transfer occurs via an adiabatic bond-stretching mechanism.