Bulk and surface polarons in photoexcited anatase TiO2

Cristiana Di Valentin, Annabella Selloni

Research output: Contribution to journalArticlepeer-review

237 Scopus citations


Using hybrid functional electronic structure calculations, we have investigated the structure and energetics of photogenerated electrons and holes in the bulk and at the (101) surface of anatase TiO2. Excitons formed upon UV irradiation are found to become self-trapped, consistent with the observation of temperature-dependent Urbach tails in the absorption spectrum and a large Stokes shift in the photoluminescence band of anatase. Electron and hole polarons are localized at Ti3+ and O- lattice sites, respectively. At the surface, the trapping sites generally correspond to undercoordinated Ti3+5c and O-2c surface atoms or to isolated OH species in the case of a hydroxylated surface. The polaron trapping energy is considerably larger at the surface than in the bulk, indicating that it is energetically favorable for the polarons to travel from the bulk to the surface. Computed one-electron energy levels in the gap and hyperfine coupling constants compare favorably with oxidation potential and EPR measurements.

Original languageEnglish (US)
Pages (from-to)2223-2228
Number of pages6
JournalJournal of Physical Chemistry Letters
Issue number17
StatePublished - Sep 1 2011

All Science Journal Classification (ASJC) codes

  • General Materials Science
  • Physical and Theoretical Chemistry


  • Energy Conversion and Storage


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