| Abstract
| - The structural, electronic, and vibrational properties of intermediates of the O2 photoreductionat the (101) TiO2 (anatase) surface have been investigated by performing ab initio density functionalcalculations. In detail, a recently proposed approach has been used where molecules on the surface aretreated like surface defects. Thus, by applying theoretical methods generally used in the physics ofsemiconductors, we successfully estimate the location and donor/acceptor character of the electronic levelsinduced by an adsorbed molecule in the TiO2 energy gap, both crucial for the surface−molecule charge-transfer processes, and investigate the formation and the properties of charged intermediates. The presentapproach permits a view of the O2 photoreduction process through several facets, which elucidates themolecule−surface charge-transfer conditions and reveals the key role played by charged intermediates. Acomparison of present results with those of a highly sensitive IR (infrared) spectroscopy study ofintermediates of the O2 photoreduction leads to a deeper understanding of this process and to revisedvibrational-line assignments and reaction paths.
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