title: Theoretical predictions of properties and volatility of chlorides and oxychlorides of group-4 elements. II. Adsorption of tetrachlorides and oxydichlorides of Zr, Hf, and Rf on neutral and modified surfaces.
abstract: With the aim to interpret results of gas-phase chromatography experiments on volatility of group-4 tetrachlorides and oxychlorides including those of Rf, adsorption enthalpies of these species on neutral, and modified quartz surfaces were estimated on the basis of relativistic, two-component Density Functional Theory calculations of MCl4, MOCl2, MCl6(-), and MOCl4(2) with the use of adsorption models. Several mechanisms of adsorption were considered. In the case of physisorption of MCl4, the trend in the adsorption energy in the group should be Zr > Hf > Rf, so that the volatility should change in the opposite direction. The latter trend complies with the one in the sublimation enthalpies, ΔH(sub), of the Zr and Hf tetrachlorides, i.e., Zr < Hf. On the basis of a correlation between these quantities, ΔH(sub)(RfCl4) was predicted as 104.2 kJ/mol. The energy of physisorption of MOCl2 on quartz should increase in the group, Zr < Hf < Rf, as defined by increasing dipole moments of these molecules along the series. In the case of adsorption of MCl4 on quartz by chemical forces, formation of the MOCl2 or MOCl4(2-) complexes on the surface can take place, so that the sequence in the adsorption energy should be Zr > Hf > Rf, as defined by the complex formation energies. In the case of adsorption of MCl4 on a chlorinated quartz surface, formation of the MCl6(2-) surface complexes can occur, so that the trend in the adsorption strength should be Zr ≤ Hf < Rf. All the predicted sequences, showing a smooth change of the adsorption energy in the group, are in disagreement with the reversed trend Zr ≈ Rf < Hf, observed in the "one-atom-at-a-time" gas-phase chromatography experiments. Thus, currently no theoretical explanation can be found for the experimental observations.
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
authors.affiliation: Department of Chemistry and Biochemistry, University of Bern, Freiestrasse 3, CH-3012 Bern, Switzerland and Laboratory for Radiochemistry and Environmental Chemistry, Paul Scherrer Institute, CH-5232 Villigen PSI, Switzerland.
authors.forename: A
authors.initials: A
authors.lastname: Türler