Ce in the +4 oxidation state: Anion photoelectron spectroscopy and photodissociation of small CexOyHz- Molecules

Josey E. Topolski, Jared O. Kafader, Caroline Chick Jarrold*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

8 Scopus citations

Abstract

The anion photoelectron (PE) spectra of a range of small mono-cerium molecular species, along with the Ce2O4- and Ce3O6- stoichiometric clusters, are presented and analyzed with the support of density functional theory calculations. A common attribute of all of the neutral species is that the Ce centers in both the molecules and clusters are in the +4 oxidation state. In bulk ceria (CeO2), an unoccupied, narrow 4f band lies between the conventional valence (predominantly O 2p) and conduction (Ce 5d) bands. Within the CeO2-, CeO3H2-, and Ce(OH)4- series, the PE spectra and computational results suggest that the Ce 6s-based molecular orbital is the singly occupied HOMO in CeO2- but becomes destabilized as the Ce 4f-local orbital becomes stabilized with increasing coordination. CeO3-, a hyperoxide, undergoes photodissociation with 3.49 eV photon energy to form the stoichiometric neutral CeO2 and O-. In the CeO2-, Ce2O4-,and Ce3O6- stoichiometric cluster series, the 6s destabilization with 4f stabilization is associated with increasing cluster size, suggesting that a bulk-like band structure may be realized with fairly small cluster sizes. The destabilization of the 6s-based molecular orbitals can be rationalized by their diffuse size relative to Ce - O bond lengths in a crystal structure, suggesting that 6s bands in the bulk may be relegated to the surface.

Original languageEnglish (US)
Article number104303
JournalJournal of Chemical Physics
Volume147
Issue number10
DOIs
StatePublished - Sep 14 2017

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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