biostudies-literatureWang LChinese Academy of SciencesAnhui Provincial Key Research and Development PlanNatural Science Foundation of Anhui ProvinceNational Natural Science Foundation of ChinaNational Key Research and Development Program of China16876-16884https://www.ebi.ac.uk/biostudies/studies/S-EPMC12371566biostudies-literatureUnknown16(36)Rutile TiO<sub>2</sub> shows great potential for photocatalytic water (H<sub>2</sub>O) splitting into oxygen (O<sub>2</sub>) and hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>). However, the mechanism of surface water oxidation on rutile TiO<sub>2</sub> remains unclear, involving complex ground-state thermal catalysis and excited-state photocatalysis processes. Here, by using linear response time-dependent density functional theory (LR-TDDFT), we investigate H<sub>2</sub>O oxidation at both the ground-state and excited-state levels. Our results show that O<sub>2</sub> formation is thermocatalytic and occurs at room temperature, while H<sub>2</sub>O<sub>2</sub> desorption is driven by photogenerated holes, requiring light to overcome a high-energy barrier, which agrees with experiments showiChemical scienceRevealing the photocatalytic dissociation of water molecules on rutile TiO<sub>2</sub> surface <i>via</i> hybrid functional based linear response time-dependent density functional theory.PMC1237156622403024221730932016YFA0200604222882012308085QB52216881022022a05020052XDB0450101CASWX2021SF-01032021YFB0300600Liu XYang JHu WLi QWang LfalseRevealing the photocatalytic dissociation of water molecules on rutile TiO<sub>2</sub> surface <i>via</i> hybrid functional based linear response time-dependent density functional theory.Rutile TiO<sub>2</sub> shows great potential for photocatalytic water (H<sub>2</sub>O) splitting into oxygen (O<sub>2</sub>) and hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>). However, the mechanism of surface water oxidation on rutile TiO<sub>2</sub> remains unclear, involving complex ground-state thermal catalysis and excited-state photocatalysis processes. Here, by using linear response time-dependent density functional theory (LR-TDDFT), we investigate H<sub>2</sub>O oxidation at both the ground-state and excited-state levels. Our results show that O<sub>2</sub> formation is thermocatalytic and occurs at room temperature, while H<sub>2</sub>O<sub>2</sub> desorption is driven by photogenerated holes, requiring light to overcome a high-energy barrier, which agrees with experiments showi2025-01-01T00:00:00Z2025 Sep2026-06-02T05:57:51.248Z2026-04-15T03:09:40.463ZS-EPMC123715664088080210.1039/d5sc02736e