Tritsaris, Georgios A. Vinichenko, Dmitry Kolesov, Grigory Friend, Cynthia M. Kaxiras, Efthimios Dynamics of the Photogenerated Hole at the Rutile TiO<sub>2</sub>(110)/Water Interface: A Nonadiabatic Simulation Study Hydrogen production in photoelectrochemical cells constitutes an important avenue toward carbon-free fuel. The most convenient process for hydrogen production is the splitting of water molecules, which necessitates a catalytic reaction involving a semiconductor. Here, we introduce a framework for the study of photocatalyzed reactions on semiconductor surfaces based on time-dependent density functional theory that explicitly accounts for the evolution of electronically excited states. Within this framework, we investigate the possibility of hole-mediated splitting of molecularly adsorbed water on a representative metal oxide surfaceî—¸the rutile TiO<sub>2</sub>(110). We find that oxidative dehydrogenation of water is possible in synergy with thermal effects at temperatures between 60 and 100 K only when defects like Ti interstitials are present in the subsurface region. This study presents a general computational strategy for describing photoexcited semiconductor/adsorbate interfaces and also demonstrates that the occurrence of water dissociation on the rutile TiO<sub>2</sub>(110) surface depends sensitively on the local atomic environment and external parameters such as temperature. splitting;Photogenerated Hole;TiO;water molecules;semiconductor surfaces;photocatalyzed reactions;oxidative dehydrogenation;hydrogen production;water dissociation;Nonadiabatic Simulation StudyHydrogen production;100 K;photoelectrochemical cells;framework;Ti interstitials;rutile 2014-11-26
    https://acs.figshare.com/articles/media/Dynamics_of_the_Photogenerated_Hole_at_the_Rutile_TiO_sub_2_sub_110_Water_Interface_A_Nonadiabatic_Simulation_Study/2231566
10.1021/jp508557w.s001