An experimental (120 K) and theoretical electron-density study of KMnO4 and KClO4.

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Bibliographic Details
Title:	An experimental (120 K) and theoretical electron-density study of KMnO4 and KClO4.
Authors:	Marabello, D.¹ domenica.marabello@unito.it, Bianchi, R.², Gervasio, G.¹, Cargnoni, F.²
Source:	Acta Crystallographica: Section A (Wiley-Blackwell). Sep2004, Vol. 60 Issue 5, p494-501. 8p. 4 Diagrams, 6 Charts.
Subjects:	Optics, Electron distribution, Electrons, X-ray diffraction, X-rays, Optical diffraction
Abstract:	The experimental electron density ρ(r) of the two isomorphic salts KMnO4 and KClO4 was determined by a multipole analysis of accurate X-ray diffraction data at 120 K. The quantum theory of atoms in molecules was applied to ρ(r) and to its Laplacian ∇²ρ(r). The bonds were characterized using the topological parameters at the bond critical points of the density ρ(r), ∇² ρ(r), G(r) (kinetic energy density), V(r) (potential energy density) and H(r) (total energy density). According to the classification recently proposed by Espinosa, Alkorta, Elguero & Molins [J. Chem. Phys. (2002), 117, 5529-5542], the K—O and Cl—O bonds have a pure ionic and covalent character, respectively, while the Mn—O bonds show an intermediate behaviour. The results of the topological analysis of the experimental and theoretical (fully periodic Hartree-Fock and density functional calculations) electron density are in good agreement, even on a quantitative level. The atomic charges, determined by performing an integration over the topological basins, are about +2 e for Mn and Cl atoms. The ionic radius, estimated with the distance of the bond critical point from the nucleus, is in agreement with a charge of +2 e for the Mn atom. [ABSTRACT FROM AUTHOR]
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Database:	Engineering Source

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Abstract:	The experimental electron density ρ(r) of the two isomorphic salts KMnO4 and KClO4 was determined by a multipole analysis of accurate X-ray diffraction data at 120 K. The quantum theory of atoms in molecules was applied to ρ(r) and to its Laplacian ∇²ρ(r). The bonds were characterized using the topological parameters at the bond critical points of the density ρ(r), ∇² ρ(r), G(r) (kinetic energy density), V(r) (potential energy density) and H(r) (total energy density). According to the classification recently proposed by Espinosa, Alkorta, Elguero & Molins [J. Chem. Phys. (2002), 117, 5529-5542], the K—O and Cl—O bonds have a pure ionic and covalent character, respectively, while the Mn—O bonds show an intermediate behaviour. The results of the topological analysis of the experimental and theoretical (fully periodic Hartree-Fock and density functional calculations) electron density are in good agreement, even on a quantitative level. The atomic charges, determined by performing an integration over the topological basins, are about +2 e for Mn and Cl atoms. The ionic radius, estimated with the distance of the bond critical point from the nucleus, is in agreement with a charge of +2 e for the Mn atom. [ABSTRACT FROM AUTHOR]
ISSN:	01087673
DOI:	10.1107/S0108767304015260