Theoretical and Experimental Chemistry

, Volume 23, Issue 4, pp 427–432 | Cite as

Electronic structure and photoelectron spectra of osmium and ruthenium tetraoxides

  • I. A. Topol'
  • V. I. Vovna
  • M. V. Kazachek
Brief Communications


The Xα-SW method has been used in the nonrelativistic and quasirelativistic approximations to calculate the electronic structures of OsO4, RuO4, and FeO4. When the 5d element is replaced by a 4d or 3d one, the electron-density redistribution is due mainly to the d electrons. All the d electrons in FeO4 are localized on the iron atom, which markedly reduces the ionic and covalent bonding on the transition from RuO4, to FeO4, which explains the instability of FeO4. The calculated spin-orbit splittings agree well with the structure of the PES bands, which enables one to establish the sequence of MO ionization energies unambiguously.


Iron Ruthenium Osmium Covalent Bonding Ionization Energy 
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Literature cited

  1. 1.
    J. E. Bloor and R. E. Sherrod, “Theoretical studies on the physical properties and bonding of the 5d metal hexafluorides using the MS Xα technique,” J. Am. Chem. Soc., 102 No. 13, 4333–4340 (1980).Google Scholar
  2. 2.
    I. M. Dyke, G. D. Josland, A. Morris, et al., “A study of the electronic structure of the actinide tetrahalides UF4, ThF4, UCl4, and ThCl4, using vacuum ultraviolet photoelectron spectroscopy and SCF-Xα scattered wave calculations,” J. Chem. Phys., 72, No 6, 3822–3827 (1980).Google Scholar
  3. 3.
    I. A. Topol' and B. I. Zhilinskii, “A guasirelativistic study of the electronic structure of uranium tetrafluoride,” Teor. Éksp. Khim., 20, No. 4, 406–415 (1984).Google Scholar
  4. 4.
    V. I. Vovna, V. V. Gorchakov, V. A. Koshelev, et al., “Photoelectron spectra and electronic structures for a series of volatile transition-metal fluorides and oxyfluorides,” Abstracts of the 7th All-Union Symposium on Inorganic-Fluoride Chemistry, Dushanbe October 9–11, 1984 [in Russian], Nauka, Moscow (1984), p. 29.Google Scholar
  5. 5.
    P. Burroughs, S. Evans, A. Hamnett, et al., “He I photoelectron spectra of some d° transition metal compounds,” J. Chem. Soc. Farad. Trans. II, 70, No. 12 1895–1911 (1974)Google Scholar
  6. 6.
    V. I. Vovna, A. S. Dudin, L. M. Avkhutskii, et al., “Photoelectron spectra and electronic structures of volatile rhenium fluorides,” Zh. Neorg. Khim., 24, No. 8, 2048–2056 (1979)Google Scholar
  7. 7.
    I. A. Topol', N. F. Stepanov, and V. M. Kovba, “An experimental and theoretical study of the electron spectra of molybdenum and tungsten oxotetrachlorides,” Teor. Éksp. Khim., 15, No. 6, 697–703 (1979).Google Scholar
  8. 8.
    I. A. Topol', V. M. Kovba, N. F. Stepanov, and A. S. Chesnyi, “A theoretical and experimental study of electron spectra of tungsten chalcogenides,” ibid., 17, No. 2, 165–171 (1981)Google Scholar
  9. 9.
    N. G. Rambidi, S. M. Tolmachev, G. I. Gurova, and I. V. Solov'eva, Five-Atom Inorganic Molecules [in Russian], Izd. Standartov, Moscow (1982).Google Scholar
  10. 10.
    F. G. Gavryuchenko (ed.), Chemistry [in Russian], Khimiya, Leningrad (1975).Google Scholar
  11. 11.
    J. G. Norman, “SCF-Xα-SW calculations in PH3 using a nonempirical scheme for choosing overlapping sphere radii,” J. Chem. Phys., 61, No. 11, 4630–4635 (1974).Google Scholar
  12. 12.
    J. H. Wood and A. M. Boring, “Improved Pauli Hamiltonian for local potential problems,” Phys. Rev. B, 18, No. 6, 2701–2711 (1978).Google Scholar
  13. 13.
    A. Rauk, T. Ziegler, and D. E. Ellis, “The electronic structure of FeO4 2−, RuO4, RuO4 , RuO4 2−, and OsO4 by the HFS-DWM method,” Theor. Chim. Acta, 34, No. 1, 49–59 (1974).Google Scholar
  14. 14.
    J. Weber, “An MS Xα study of the electronic structure of osmium tetraoxide,” Chem. Phys. Lett., 45, No. 2, 261–264 (1977).Google Scholar
  15. 15.
    D. A. Case and M. Karplus, “The calculation of the one electron properties from Xα multiple scattering wave functions,” Chem. Phys. Lett., 39, No. 1, 33–38 (1976).Google Scholar
  16. 16.
    L. S. Cederbaum and W. Domcke, “Theoretical aspects of ionization potentials and photoelectron spectroscopy: a Green's function approach,” Adv. Chem. Phys., 36, 205–344 (1977).Google Scholar
  17. 17.
    A. V. Kondratenko, L. N. Mazalov, and I. A. Topol', Highly Excited States in Molecules [in Russian], Nauka, Novosibirsk (1982).Google Scholar

Copyright information

© Plenum Publishing Corporation 1988

Authors and Affiliations

  • I. A. Topol'
    • 1
    • 2
  • V. I. Vovna
    • 1
    • 2
  • M. V. Kazachek
    • 1
    • 2
  1. 1.Far East UniversityVladivostok
  2. 2.All-Union Center for Research on Surface and Vacuum PropertiesMoscow

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