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A mapping of the electron localization function for earth materials

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Abstract

The electron localization function, ELF, generated for a number of geometry-optimized earth materials, provides a graphical representation of the spatial localization of the probability electron density distribution as embodied in domains ascribed to localized bond and lone pair electrons. The lone pair domains, displayed by the silica polymorphs quartz, coesite and cristobalite, are typically banana-shaped and oriented perpendicular to the plane of the SiOSi angle at ~0.60 Å from the O atom on the reflex side of the angle. With decreasing angle, the domains increase in magnitude, indicating an increase in the nucleophilic character of the O atom, rendering it more susceptible to potential electrophilic attack. The Laplacian isosurface maps of the experimental and theoretical electron density distribution for coesite substantiates the increase in the size of the domain with decreasing angle. Bond pair domains are displayed along each of the SiO bond vectors as discrete concave hemispherically-shaped domains at ~0.70 Å from the O atom. For more closed-shell ionic bonded interactions, the bond and lone pair domains are often coalesced, resulting in concave hemispherical toroidal-shaped domains with local maxima centered along the bond vectors. As the shared covalent character of the bonded interactions increases, the bond and lone pair domains are better developed as discrete domains. ELF isosurface maps generated for the earth materials tremolite, diopside, talc and dickite display banana-shaped lone pair domains associated with the bridging O atoms of SiOSi angles and concave hemispherical toroidal bond pair domains associated with the nonbridging ones. The lone pair domains in dickite and talc provide a basis for understanding the bonded interactions between the adjacent neutral layers. Maps were also generated for beryl, cordierite, quartz, low albite, forsterite, wadeite, åkermanite, pectolite, periclase, hurlbutite, thortveitite and vanthoffite. Strategies are reviewed for finding potential H docking sites in the silica polymorphs and related materials. As observed in an earlier study, the ELF is capable of generating bond and lone pair domains that are similar in number and arrangement to those provided by Laplacian and deformation electron density distributions. The formation of the bond and lone pair domains in the silica polymorphs and the progressive decrease in the SiO length as the value of the electron density at the bond critical point increases indicates that the SiO bonded interaction has a substantial component of covalent character.

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Acknowledgements

The National Science Foundations (Grants EAR-0229472, NLR and GVG), The US Department of Energy (Grant DE-FG02-03Er14751, JD Rimstidt and GVG) and The Chemical Sciences, Geosciences, Office of Basic Energy Sciences (Grant DE-FG02-97ER14751, DFC) are thanked for generously supporting this work. This study was also generously supported by the National Computational Science Alliance under a SURA Block Grant (Project ndg), utilizing the IBM p690 at the National Center for Supercomputing Applications. Dr. Robert T. Downs of the University of Arizona reviewed the paper and is thanked for making a number of valuable suggestions that improved the paper.

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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

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

    D. F. Cox

  3. Department of Geosciences, Virginia Tech, Blacksburg, VA, 24061, USA

    N. L. Ross & J. B. Burt

  4. Department of Chemistry, Virginia Tech, Blacksburg, VA, 24061, USA

    T. D. Crawford

  5. W.R.Wiley Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, WA, 99352

    K. M. Rosso

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  1. G. V. Gibbs
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Correspondence to G. V. Gibbs.

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Gibbs, G.V., Cox, D.F., Ross, N.L. et al. A mapping of the electron localization function for earth materials. Phys Chem Minerals 32, 208–221 (2005). https://doi.org/10.1007/s00269-005-0463-x

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