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Thioarsenides: a case for long-range Lewis acid–base-directed van der Waals interactions

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Abstract

Electron density distributions, bond paths, Laplacian and local-energy density properties have been calculated for a number of As4S n (n = 3, 4 and 5) thioarsenide molecular crystals. On the basis of the distributions, the intramolecular As–S and As–As interactions classify as shared bonded interactions, and the intermolecular As–S, As–As and S–S interactions classify as closed-shell van der Waals (vdW) bonded interactions. The bulk of the intermolecular As–S bond paths link regions of locally concentrated electron density (Lewis-base regions) with aligned regions of locally depleted electron density (Lewis-acid regions) on adjacent molecules. The paths are comparable with intermolecular paths reported for several other molecular crystals that link aligned Lewis base and acid regions in a key–lock fashion, interactions that classified as long-range Lewis acid–base-directed vdW interactions. As the bulk of the intermolecular As–S bond paths (~70%) link Lewis acid–base regions on adjacent molecules, it appears that molecules adopt an arrangement that maximizes the number of As–S Lewis acid–base intermolecular bonded interactions. The maximization of the number of Lewis acid–base interactions appears to be connected with the close-packed array adopted by molecules: distorted cubic close-packed arrays are adopted for alacránite, pararealgar, uzonite, realgar and β-AsS and the distorted hexagonal close-packed arrays adopted by α- and β-dimorphite. A growth mechanism is proposed for thioarsenide molecular crystals from aqueous species that maximizes the number of long-range Lewis acid–base vdW As–S bonded interactions with the resulting directed bond paths structuralizing the molecules as a molecular crystal.

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Acknowledgments

The National Science Foundation and the US Department of Energy are thanked for supporting this study with Grants EAR-0609885 (N.L.R. and G.V.G.), EAR-0609906 (R.T.D.), and DE-FG02-97ER14751 (D.F.C.). K.M.R. acknowledges a grant from the US Department of Energy (DOE), Office of Basic Energy Sciences, Geoscience Division and computational facilities and support from the Environmental Molecular Sciences Laboratory (EMSL) at the Pacific Northwest National Laboratory (PNNL). The computations were performed in part at the EMSL at PNNL. The EMSL is a national scientific user facility sponsored by the US DOE Office of Biological and Environmental Research. PNNL is operated by Battelle for the DOE under contract DEAC06-76RLO 1830. GVG wishes to thank his good friend and colleague Professor Michael Hochella for reading a preliminary draft of the manuscript and contributing to the discussion of the growth mechanism for a thioarsenide molecular crystal that maximizes the number of long-range Lewis acid–base vdW As–S bonded interactions. He also wishes to thank Professors Richard F. W. Bader at McMaster University, Ontario, Canada and Vladimir Tsirelson at Mendelev University of Chemical Technology, Moscow, Russia for useful discussions related to van der Waals bonded interactions. We also want to thank Professor Emil Makovicky at University of Copenhagen, Copenhagen, Denmark for his careful review of the manuscript, his suggested changes and his insightful comments on the connection between micelles and directed bond paths.

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Authors and Affiliations

  1. Departments of Geosciences, Materials Science and Engineering and Mathematics, Virginia Tech, Blacksburg, VA, 24061, USA

    G. V. Gibbs & N. L. Ross

  2. Earth Science Division, Lawrence Berkeley National Laboratory, Berkeley, CA, 94720, USA

    A. F. Wallace

  3. Department of Geosciences, University of Arizona, Tucson, AZ, 85721, USA

    R. T. Downs

  4. Department of Chemical Engineering, Virginia Tech, Blacksburg, VA, 24061, USA

    D. F. Cox

  5. Chemical and Materials Science Division, W.R. Wiley Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, WA, 99352, USA

    K. M. Rosso

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  1. G. V. Gibbs
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Gibbs, G.V., Wallace, A.F., Downs, R.T. et al. Thioarsenides: a case for long-range Lewis acid–base-directed van der Waals interactions. Phys Chem Minerals 38, 267–291 (2011). https://doi.org/10.1007/s00269-010-0402-3

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