Pershina V, Bastug T, Fricke B
Gesellschaft für Schwerionenforschung, D-64291 Darmstadt, Germany.
J Chem Phys. 2005 Mar 22;122(12):124301. doi: 10.1063/1.1862241.
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 HsO4 than in the lighter congeners. Relativistic effects were also shown to slightly decrease dispersion interaction energies of RuO4, OsO4, and HsO4 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<HsO4. The reason for that is identical trends in the relativistic and nonrelativistic space distributions of the valence d electrons.
基于全相对论（四分量）和非相对论密度泛函理论计算结果，研究了相对论效应对第8族四氧化物MO₄（其中M = Ru、Os和108号元素Hs）性质和挥发性的影响。结果表明，相对论效应会增强这些分子中的键强度并缩短键长。它们导致分子极化率降低，电离势增加。这些效应在HsO₄中比在较轻的同系物中要强得多。相对论效应还表明会略微降低RuO₄、OsO₄和HsO₄与惰性（石英或氮化硅）表面的色散相互作用能，即，在“一次一个原子”的气相色谱实验中所研究的那样，它们会增加这些化合物的挥发性。然而，它们并不影响第8族中的趋势：无论是相对论还是非相对论情况下，挥发性都应按RuO₄<OsO₄<HsO₄的顺序变化。其原因是价d电子的相对论和非相对论空间分布具有相同的趋势。
