Abstract
This study examines the electron localization function (ELF) isosurfaces of the Al2SiO5 polymorphs kyanite, sillimanite, and andalusite to see how differences in coordination and geometry of the cations and anions affect the ELF isosurfaces. Examination of the ELF isosurfaces indicates that their shapes are dependent on the coordination and geometry of the oxygen atoms and are not sensitive to coordination of the surrounding cations. Of the 18 crystallographically distinct oxygen atoms in the Al2SiO5 polymorphs, 13 are bonded to two aluminum atoms and one silicon atom (Al2–O–Si) and are associated with two different ELF isosurface shapes. The shape of the ELF isosurface is dependent on the distance at which the oxygen atom lies from a plane defined by the three surrounding cations: at a distance greater than 0.2 Å the ELF can be defined as horseshoe-shaped and at a distance less then 0.2 Å it can be described as concave hemispherical. This feature is also seen in the ELF isosurfaces for the oxygens bonded to three aluminum atoms (Al3–O) where the isosurfaces can be defined as trigonally toroidal and uniaxially trigonally toroidal. The changes in the ELF isosurfaces for the three coordinated oxygens are also indicative of changes in hybridization. The ELF isosurface for the two-fold coordinated oxygen (Al–O–Si) has a large mushroom-shaped isosurface along the Al–O bond and a concave hemispherical isosurface along the Si–O. The four-fold coordinated oxygen (Al4–O) contains two concave hemispherical isosurfaces along the shorter Al–O bonds and a banana-shaped isosurface, which encompasses the longer Al–O bonds. In addition, this study shows the homeomorphic relationship between the ELF isosurfaces and electron density difference maps with respect to number and arrangement of domains.
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Acknowledgments
This study was 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 and by the National Science Foundation (Grant EAR-0229472 to NLR and GVG).
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Burt, J.B., Gibbs, G.V., Cox, D.F. et al. ELF isosurface maps for the Al2SiO5 polymorphs. Phys Chem Minerals 33, 138–144 (2006). https://doi.org/10.1007/s00269-006-0062-5
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DOI: https://doi.org/10.1007/s00269-006-0062-5