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The essential role of charge-shift bonding in hypervalent prototype XeF2

Nature Chemistry volume 5, pages 417–422 (2013)Cite this article

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An Erratum to this article was published on 20 November 2015

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Abstract

Hypervalency in XeF2 and isoelectronic complexes is generally understood in terms of the Rundle–Pimentel model (which invokes a three-centre/four-electron molecular system) or its valence bond version as proposed by Coulson, which replaced the old expanded octet model of Pauling. However, the Rundle–Pimentel model is not always successful in describing such complexes and has been shown to be oversimplified. Here using ab initio valence bond theory coupled to quantum Monte Carlo methods, we show that the Rundle–Pimentel model is insufficient by itself in accounting for the great stability of XeF2, and that charge-shift bonding, wherein the large covalent–ionic interaction energy has the dominant role, is a major stabilizing factor. The energetic contribution of the old expanded octet model is also quantified and shown to be marginal. Generalizing to isoelectronic systems such as ClF3, SF4, PCl5 and others, it is suggested that charge-shift bonding is necessary, in association with the Rundle–Pimentel model, for hypervalent analogues of XeF2 to be strongly bonded.

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Figure 1: The Rundle–Pimentel orbital model for 3c–4e hypervalent complexes.
Figure 2: The three VB structures of F–Xe+ and their weights as calculated by the BOVB (upper line) and VB–VMC (lower line) methods, in the ps-VTZ basis set.
Figure 3: VB structures of XeF2 and their weights, as calculated at the VB–VMC/ps-VTZ level.

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Change history

  • 09 October 2015

    This Article was accepted on 28 February 2013. This information appeared incorrectly in the original versions of this Article and has now been corrected in the online versions.

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Acknowledgements

The authors thank W. Wu and C.J. Umrigar for respectively making their XMVB and CHAMP code available to us.

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Authors and Affiliations

  1. UPMC Université Paris 06, CNRS UMR 7616, Laboratoire de Chimie Théorique, C. 137, 4 Place Jussieu, Paris Cedex 05, 75252, France

    Benoît Braïda

  2. Laboratoire de Chimie Physique, UMR CNRS 8000, Université de Paris Sud, Orsay Cédex, 91405, France

    Philippe C. Hiberty

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Contributions

Both authors designed the project. B.B. performed all the calculations. Both authors analysed the data. P.C.H. wrote the manuscript and the Supplementary Information. Both authors discussed the results and commented on the manuscript.

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Correspondence to Benoît Braïda or Philippe C. Hiberty.

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Braïda, B., Hiberty, P. The essential role of charge-shift bonding in hypervalent prototype XeF2. Nature Chem 5, 417–422 (2013). https://doi.org/10.1038/nchem.1619

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