000517619 001__ 517619 000517619 005__ 20250715173103.0 000517619 0247_ $$2doi$$a10.1103/PhysRevLett.130.108001 000517619 0247_ $$2datacite_doi$$a10.3204/PUBDB-2023-00580 000517619 0247_ $$2altmetric$$aaltmetric:143247336 000517619 0247_ $$2pmid$$a36962043 000517619 0247_ $$2WOS$$aWOS:000982435900009 000517619 0247_ $$2openalex$$aopenalex:W4323310708 000517619 037__ $$aPUBDB-2023-00580 000517619 041__ $$aEnglish 000517619 082__ $$a530 000517619 1001_ $$0P:(DE-H253)PIP1083077$$aWagstaffe, Michael$$b0$$eCorresponding author 000517619 245__ $$aPhotoinduced dynamics at the water/TiO$_2$(101) interface 000517619 260__ $$aCollege Park, Md.$$bAPS$$c2023 000517619 3367_ $$2DRIVER$$aarticle 000517619 3367_ $$2DataCite$$aOutput Types/Journal article 000517619 3367_ $$0PUB:(DE-HGF)16$$2PUB:(DE-HGF)$$aJournal Article$$bjournal$$mjournal$$s1718785072_3773429 000517619 3367_ $$2BibTeX$$aARTICLE 000517619 3367_ $$2ORCID$$aJOURNAL_ARTICLE 000517619 3367_ $$00$$2EndNote$$aJournal Article 000517619 520__ $$aWe present a femtosecond time-resolved optical pump-soft x-ray probe photoemission study in which we follow the dynamics of charge transfer at the interface of water and anatase TiO$_2$(101). By combining our observation of transient oxygen O 1s core level peak shifts at submonolayer water coverages with Ehrenfest molecular dynamics simulations we find that ultrafast interfacial hole transfer from TiO$_2$ to molecularly adsorbed water is completed within the 285 fs time resolution of the experiment. This is facilitated by the formation of a new hydrogen bond between an O$_2$c site at the surface and a physisorbed water molecule. The calculations fully corroborate our experimental observations and further suggest that this process is preceded by the efficient trapping of the hole at the surface of TiO$_2$ by hydroxyl species (-OH), that form following the dissociative adsorption of water. At a water coverage exceeding a monolayer, interfacial charge transfer is suppressed. 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