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The structure of the SF6 molecule and the SF −6 anion excited states

  • Physical Chemistry
  • Structure And Physicochemical Properties Of Molecules
  • Published:
Bulletin of the Russian Academy of Sciences, Division of chemical science Aims and scope

Abstract

The electronic and geometric structures of the ground state and a number of excited states of the SF6 molecule and the SF −6 anion have been calculated by the discrete-variation method of the local density-functionals. The anion was found to possess a number of states stable toward the outer electron detachment, and at least one excited state stable toward dissociation. The adiabatic electron affinity (EA) was determined as 3.46 eV at the highest level of theory. This result is correlated to the high EAs of the isovalent compound SeF6 and TeF6; however, it does not agree with the presently accepted experimental estimate of 1.0 ± 0.2 eV for the SF6EA value. The basic anion configuration is octahedral with a S-F bond length of 1.717 Å. The calculated limit for the highest dissociation channel of the ground state SF −6 → SF −5 + F is ≈ 1.5 eV lower than the minimum of the total energy of the neutral molecule; this is in good agreement with experimental estimates.

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  1. G. L. Gutsev
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Additional information

Institute for Chemical Physics, Russian Academy of Sciences, 142432 Chernogolovka. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 3, pp. 641–649, March, 1992.

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Gutsev, G.L. The structure of the SF6 molecule and the SF −6 anion excited states. Russ Chem Bull 41, 504–510 (1992). https://doi.org/10.1007/BF00863073

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  • DOI: https://doi.org/10.1007/BF00863073

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