Molecular geometries and relative stabilities of titanium oxide and gold-titanium oxide clusters

Titanium oxide and gold-titanium oxide clusters of stoichiometry MxOy (M-x = Ti-3, Ti-4 & AuTi3; y = 0 - (2x + 2)) have been investigated using density functional theory. Geometries of determined global energy minimum structures are reported and other isomers predicted up to 0.5 eV higher in energy. The Ti3On geometries build upon a triangular Ti-3 motif, while Ti4On stoichiometries template upon a pseudo-tetrahedral Ti-4 structure. Addition of a gold atom to the Ti3On series does not significantly alter the cluster geometry, with the gold atom preferentially binding to titanium atoms over oxygen atoms. Adiabatic ionization energies, electron affinities and HOMO/LUMO energies increase in magnitude with increasing oxygenation. The HOMO-LUMO energy gaps reach the bulk anatase band gap energy at stoichiometry (Au)TimO(2m-1), and increase above this upon further oxygen addition. The most stable structural moieties are found to be a cage-like, C-3v symmetric Ti4O6/7 geometry and a Ti3O6 structure with an eta(3)-bound oxygen atom. (C) 2016 Elsevier B. V. All rights reserved.