title: Theoretical predictions of properties and volatility of chlorides and oxychlorides of group-4 elements. I. Electronic structures and properties of MCl₄ and MOCl₂ (M = Ti, Zr, Hf, and Rf).
abstract: Relativistic, infinite order exact two-component, density functional theory electronic structure calculations were performed for MCl4 and MOCl2 of group-4 elements Ti, Zr, Hf, and element 104, Rf, with the aim to predict their behaviour in gas-phase chromatography experiments. RfCl4 and RfOCl2 were shown to be less stable than their lighter homologs in the group, tetrachlorides and oxychlorides of Zr and Hf, respectively. The oxychlorides turned out to be stable as a bent structure, though the stabilization energy with respect to the flat one (C(2v)) is very small. The trend in the formation of the tetrachlorides from the oxychlorides in group 4 is shown to be Zr < Hf < Rf, while the one in the formation of the oxychlorides from the chlorides is opposite. All the calculated properties are used to estimate adsorption energy of these species on various surfaces in order to interpret results of gas-phase chromatography experiments, as is shown in Paper II.
authors.affiliation: GSI Helmholtzzentrum für Schwerionenforschung, Planckstr. 1, Darmstadt D-64291, Germany.
authors.forename: V
authors.initials: V
authors.lastname: Pershina
authors.affiliation: Helmholtz Institute Mainz, Mainz D-55128, Germany and Centre for Theoretical Chemistry and Physics, New Zealand Institute for Advanced Study, Massey University, Private Bag 102904, 0745 North Shore MSC, Auckland, New Zealand.
authors.forename: A
authors.initials: A
authors.lastname: Borschevsky
authors.affiliation: Department of Chemistry, Faculty of Natural Sciences, Matej Bel University, Tajovského 40, SK-974 00 Banská Bystrica, Slovakia.
authors.forename: M
authors.initials: M
authors.lastname: Iliaš