title: Solvation of Ti(IV) in aqueous solution under ambient and supercritical conditions.
abstract: We examine the structure of the hydrated Ti(IV) complex under both ambient and supercritical conditions using first-principles molecular dynamics. We find that an unanticipated fivefold coordination of Ti(IV) is favoured under ambient conditions, with rapid interconversions between square pyramidal and trigonal bipyramidal structures. At supercritical conditions the Ti coordination increases from five to six, adopting both octahedral and trigonal prismatic geometries. At 1000 K, the magnitude of the increase in the Ti to oxygen coordination number with increasing water density is similar to that of Li-O under comparable conditions. We present a detailed picture of the bonding in the hydrated Ti(IV) complex under both ambient and supercritical conditions.
authors.affiliation: VU University Amsterdam, Faculty of Earth and Life Sciences, 1081HV, Amsterdam, The Netherlands. jelle.van.sijl@falw.vu.nl
authors.forename: Jelle
authors.initials: J
authors.lastname: van Sijl
authors.forename: Neil L
authors.initials: NL
authors.lastname: Allan
authors.forename: Gareth R
authors.initials: GR
authors.lastname: Davies
authors.forename: Wim
authors.initials: W
authors.lastname: van Westrenen
mesh_terms: D056831:Coordination Complexes / Q000737:chemistry; D056004:Molecular Dynamics Simulation; D011789:Quantum Theory; D012997:Solvents / Q000737:chemistry*; D014025:Titanium / Q000737:chemistry*; D014867:Water / Q000737:chemistry
chemical_list: D056831:Coordination Complexes; D012997:Solvents; D014867:Water; D014025:Titanium