Dependence of the lone pair of bismuth on coordination environment and pressure: An ab initio study on Cu{sub 4}Bi{sub 5}S{sub 10} and Bi{sub 2}S{sub 3}

Journal Article · Wed Sep 15 04:00:00 EDT 2010 · Journal of Solid State Chemistry

DOI:https://doi.org/10.1016/j.jssc.2010.07.022· OSTI ID:21483673

Lopez-Solano, Javier ^[1]; Garcia, Alberto ^[2]; Balic-Zunic, Tonci; Makovicky, Emil ^[3]

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1. Departamento Fisica de la Materia Condensada, Universidad del Pais Vasco, 48080 Bilbao (Spain)
2. Institut de Ciencia de Materials de Barcelona (ICMAB-CSIC), Campus UAB, 08193 Bellaterra (Spain)
3. Department of Geography and Geology, University of Copenhagen, 1350 Copenhagen (Denmark)

DFT calculations have been carried out for Cu{sub 4}Bi{sub 5}S{sub 10} and Bi{sub 2}S{sub 3} to provide an analysis of the relation between electronic structure, lone electron pairs and the local geometry. The effect of pressure is considered in Bi{sub 2}S{sub 3} and the results are compared to published experimental data. Bi{sup 3+} in Cu{sub 4}Bi{sub 5}S{sub 10} is found at both symmetrically and asymmetrically coordinated sites, whereas the coordination environments of Bi in Bi{sub 2}S{sub 3} are asymmetric at room conditions and get more regular with increasing pressure. The charge density maps of the asymmetric sites show the lone pairs as lobes of non-shared charge. These lobes are related to an effective Bi s-Bi p hybridization resulting from coupling to S p orbitals, supporting the modern view of the origin of the stereochemically active lone pair. No effective Bi s-p hybridization is seen for the symmetric site in Cu{sub 4}Bi{sub 5}S{sub 10}, whereas Bi s-p hybridization coexists with a much reduced lone pair in Bi{sub 2}S{sub 3} at high pressure. - Graphical abstract: The article includes charge density maps used to analyze the charge distribution around bismuth in sulfides. This map shows the orientation of a lone electron pair.

• OSTI ID: 21483673
• Journal Information: Journal of Solid State Chemistry, Journal Name: Journal of Solid State Chemistry Journal Issue: 9 Vol. 183; ISSN 0022-4596; ISSN JSSCBI
• Country of Publication: United States
• Language: English

Related Subjects

36 MATERIALS SCIENCE
ASYMMETRY
BISMUTH COMPOUNDS
BISMUTH IONS
BISMUTH SULFIDES
CHALCOGENIDES
CHARGE DENSITY
CHARGE DISTRIBUTION
CHARGED PARTICLES
COPPER COMPOUNDS
COUPLING
ELECTRON PAIRS
ELECTRONIC STRUCTURE
HYBRIDIZATION
IONS
ORIENTATION
SULFIDES
SULFUR COMPOUNDS
TRANSITION ELEMENT COMPOUNDS