title: Electron density distributions calculated for the nickel sulfides millerite, vaesite, and heazlewoodite and nickel metal: a case for the importance of ni-ni bond paths for electron transport.
abstract: Bond paths and the bond critical point properties (the electron density (rho) and the Hessian of rho at the bond critical points (bcp's)) have been calculated for the bonded interactions comprising the nickel sulfide minerals millerite, NiS, vaesite, NiS(2), and heazlewoodite, Ni(3)S(2), and Ni metal. The experimental Ni-S bond lengths decrease linearly as the magnitudes of the properties each increases in value. Bond paths exist between the Ni atoms in heazlewoodite and millerite for the Ni-Ni separations that match the shortest separation in Ni metal, an indicator that the Ni atoms are bonded. The bcp properties of the bonded interactions in Ni metal are virtually the same as those in heazlewoodite and millerite. Ni-Ni bond paths are absent in vaesite where the Ni-Ni separations are 60% greater than those in Ni metal. The bcp properties for the Ni-Ni bonded interactions scatter along protractions of the Ni-S bond length-bcp property trends, suggesting that the two bonded interactions have similar characteristics. Ni-Ni bond paths radiate throughout Ni metal and the metallic heazlewoodite structures as continuous networks whereas the Ni-Ni paths in millerite, a p,d-metal displaying ionic and covalent features, are restricted to isolated Ni(3) rings. Electron transport in Ni metal and heazlewoodite is pictured as occurring along the bond paths, which behave as networks of atomic size wires that radiate in a contiguous circuit throughout the two structures. Unlike heazlewoodite, the electron transport in millerite is pictured as involving a cooperative hopping of the d-orbital electrons from the Ni(3) rings comprising Ni(3)S(9) clusters to Ni(3) rings in adjacent clusters via the p-orbitals on the interconnecting S atoms. Vaesite, an insulator at low temperatures and a doped semiconductor at higher temperatures, lacks Ni-Ni bond paths. The net charges conferred on the Ni and S atoms are about a quarter of their nominal charges for the atoms in millerite and vaesite with the net charge on Ni increasing with increasing Ni-S bond length. Reduced net charges are observed on the Ni atoms in heazlewoodite and are related to its Ni-Ni metal bonded interactions and to the greater covalent character of its bonds. Local energy density and bond critical point properties of the electron density distributions indicate that the Ni-S and Ni-Ni bonded interactions are intermediate in character between ionic and covalent.
authors.affiliation: Departments of Geosciences, Materials Science and Engineering, Chemical Engineering, and Mathematics, Virginia Tech, Blacksburg, Virginia 24061, USA. gvgibbs@vt.edu
authors.forename: G V
authors.initials: GV
authors.lastname: Gibbs
authors.forename: R T
authors.initials: RT
authors.lastname: Downs
authors.forename: C T
authors.initials: CT
authors.lastname: Prewitt
authors.forename: K M
authors.initials: KM
authors.lastname: Rosso
authors.forename: N L
authors.initials: NL
authors.lastname: Ross
authors.forename: D F
authors.initials: DF
authors.lastname: Cox