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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)

Pershina, V., Borschevsky, A. & Ilias, M., 14-Aug-2014, In : Journal of Chemical Physics. 141, 6, 8 p., 064314.

Research output: Contribution to journalArticleAcademicpeer-review

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. RfCl(4) and RfOCl(2) 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. 

Original languageEnglish
Article number064314
Number of pages8
JournalJournal of Chemical Physics
Volume141
Issue number6
Publication statusPublished - 14-Aug-2014
Externally publishedYes

    Keywords

  • DENSITY-FUNCTIONAL THEORY, RELATIVISTIC DOUBLE-ZETA, BOND COVALENT RADII, BASIS-SETS, TRANSACTINIDE ELEMENTS, ENERGY CALCULATIONS, TRANSITION-METALS, HEAVIEST ELEMENTS, TRIPLE-ZETA, CHEMISTRY

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