Stretching vibration driven adiabatic transfer kinetics for photoexcited hole transfer from semiconductor to adsorbate.

ABSTRACT: 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 hi

SUBMITTER: Zhou M 

PROVIDER: S-EPMC11479618 | biostudies-literature | 2024 Oct

REPOSITORIES: biostudies-literature