The influence of relativistic effects on properties and volatility of the group-8 tetroxides MO4, where M=Ru, Os, and element 108, Hs, was studied on the basis of results of the fully relativistic (four component) and nonrelativistic density functional theory calculations. Relativistic effects were shown to increase bond strengths and decrease bond lengths in these molecules. They are responsible for a decrease in molecular polarizabilities and an increase in ionization potentials. The effects are much stronger in HsO(4) than in the lighter congeners. Relativistic effects were also shown to slightly decrease dispersion interaction energies of RuO4, OsO4, and HsO(4) with an inert (quartz or silicon nitride) surface, i.e., they increase volatility of these compounds as studied in the one-atom-at-a-time gas-phase chromatography experiments. They do, however, not influence the trend in group 8: both relativistically and nonrelativistically, volatility should change as RuO4< OsO4< HsO(4). The reason for that is identical trends in the relativistic and nonrelativistic space distributions of the valence d electrons.
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