Chemical Bonding in Octahedral XeF6 and SF6*

Matthias Lein; Gernot Frenking

doi:10.1071/CH04113

RESEARCH ARTICLE

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Chemical Bonding in Octahedral XeF₆ and SF₆^*

Matthias Lein ^A and Gernot Frenking ^A ^B

+ Author Affiliations

- Author Affiliations

^A Fachbereich Chemie, Philipps-Universität Marburg, 35032 Marburg, Germany.

^B Corresponding author. Email: frenking@chemie.uni-marburg.de

Australian Journal of Chemistry 57(12) 1191-1195 https://doi.org/10.1071/CH04113
Submitted: 30 April 2004 Accepted: 8 November 2004 Published: 8 December 2004

Abstract

Quantum chemical density functional theory calculations have been carried out for octahedral XeF₆ and SF₆ at the BP86/TZ2P level with relativistic effects included by the ZORA approximation. The energy decomposition analysis of XeF₆ and SF₆ using neutral and charged fragments EF₅ + F and EF₅⁺ + F⁻ as well as E + F₆ and E⁶⁺ + F₆⁶⁻ indicates that the dominant E–F orbital interactions take place between σ-orbitals which have t_1u symmetry in the octahedral point group. The contribution of the a_1g orbitals is negligible in the 16 valence electron compound XeF₆. The a_1g contribution becomes larger in the 14 valence electron species SF₆ but it is less important than the t_1u term. The bonding between the neutral species comes mainly from covalent (orbital) interactions but the quasiclassical electrostatic attraction significantly contributes to the attractive interactions. The bonding which comes from the ΔE_orb term is compensated by the Pauli repulsion ΔE_Pauli. The sum of ΔE_orb and ΔE_Pauli is repulsive for XeF₆ and SF₆, which would not be stable molecules without quasiclassical electrostatic attraction.

Acknowledgments

This work was supported by the Deutsche Forschungsgemeinschaft. Excellent service by the Hochschulrechenzentrum of the Philipps-Universität Marburg is gratefully acknowledged. Additional computer time was provided by the HLRS Stuttgart, HLR Darmstadt, and the CSC Frankfurt.

References

^* Theoretical studies of inorganic compounds. Part 32. Part 31: C. Esterhuysen, G. Frenking, Theoret. Chem. Acc. 2004, 111, 381. doi:10.1007/S00214-003-0535-2

Chemical Bonding in Octahedral XeF6 and SF6*

Abstract

Acknowledgments

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Chemical Bonding in Octahedral XeF₆ and SF₆^*