Dependence of the lone pair of bismuth on coordination environment and pressure: an ab initio study on Cu4Bi5S10 and Bi2S3

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Dependence of the lone pair of bismuth on coordination environment and pressure : an ab initio study on Cu4Bi5S10 and Bi2S3. / Olsen, Lars Arnskov; López-Solano, Javier; García, Alberto; Balic Zunic, Tonci; Makovicky, Emil.

In: Journal of Solid State Chemistry, Vol. 183, No. 9, 2010, p. 2133-2143.

Research output: Contribution to journal › Journal article › Research › peer-review

Harvard

Olsen, LA, López-Solano, J, García, A, Balic Zunic, T & Makovicky, E 2010, 'Dependence of the lone pair of bismuth on coordination environment and pressure: an ab initio study on Cu4Bi5S10 and Bi2S3', Journal of Solid State Chemistry, vol. 183, no. 9, pp. 2133-2143. https://doi.org/10.1016/j.jssc.2010.07.022

APA

Olsen, L. A., López-Solano, J., García, A., Balic Zunic, T., & Makovicky, E. (2010). Dependence of the lone pair of bismuth on coordination environment and pressure: an ab initio study on Cu4Bi5S10 and Bi2S3. Journal of Solid State Chemistry, 183(9), 2133-2143. https://doi.org/10.1016/j.jssc.2010.07.022

Vancouver

Olsen LA, López-Solano J, García A, Balic Zunic T, Makovicky E. Dependence of the lone pair of bismuth on coordination environment and pressure: an ab initio study on Cu4Bi5S10 and Bi2S3. Journal of Solid State Chemistry. 2010;183(9):2133-2143. https://doi.org/10.1016/j.jssc.2010.07.022

Author

Olsen, Lars Arnskov ; López-Solano, Javier ; García, Alberto ; Balic Zunic, Tonci ; Makovicky, Emil. / Dependence of the lone pair of bismuth on coordination environment and pressure : an ab initio study on Cu4Bi5S10 and Bi2S3. In: Journal of Solid State Chemistry. 2010 ; Vol. 183, No. 9. pp. 2133-2143.

Bibtex

@article{225e0b92a0d4424eb3eedb5be1192c28,
title = "Dependence of the lone pair of bismuth on coordination environment and pressure: an ab initio study on Cu4Bi5S10 and Bi2S3",
abstract = "DFT calculations have been carried out for Cu4Bi5S10 and Bi2S3 to provide an analysis of the relation between electronic structure, lone electron pairs and the local geometry. The effect of pressure is considered in Bi2S3 and the results are compared to published experimental data. Bi3+ in Cu4Bi5S10 is found at both symmetrically and asymmetrically coordinated sites, whereas the coordination environments of Bi in Bi2S3 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 Cu4Bi5S10, whereas Bi s–p hybridization coexists with a much reduced lone pair in Bi2S3 at high pressure.",
author = "Olsen, {Lars Arnskov} and Javier L{\'o}pez-Solano and Alberto Garc{\'i}a and {Balic Zunic}, Tonci and Emil Makovicky",
year = "2010",
doi = "10.1016/j.jssc.2010.07.022",
language = "English",
volume = "183",
pages = "2133--2143",
journal = "Journal of Solid State Chemistry",
issn = "0022-4596",
publisher = "Academic Press",
number = "9",

}

RIS

TY - JOUR

T1 - Dependence of the lone pair of bismuth on coordination environment and pressure

T2 - an ab initio study on Cu4Bi5S10 and Bi2S3

AU - Olsen, Lars Arnskov

AU - López-Solano, Javier

AU - García, Alberto

AU - Balic Zunic, Tonci

AU - Makovicky, Emil

PY - 2010

Y1 - 2010

N2 - DFT calculations have been carried out for Cu4Bi5S10 and Bi2S3 to provide an analysis of the relation between electronic structure, lone electron pairs and the local geometry. The effect of pressure is considered in Bi2S3 and the results are compared to published experimental data. Bi3+ in Cu4Bi5S10 is found at both symmetrically and asymmetrically coordinated sites, whereas the coordination environments of Bi in Bi2S3 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 Cu4Bi5S10, whereas Bi s–p hybridization coexists with a much reduced lone pair in Bi2S3 at high pressure.

AB - DFT calculations have been carried out for Cu4Bi5S10 and Bi2S3 to provide an analysis of the relation between electronic structure, lone electron pairs and the local geometry. The effect of pressure is considered in Bi2S3 and the results are compared to published experimental data. Bi3+ in Cu4Bi5S10 is found at both symmetrically and asymmetrically coordinated sites, whereas the coordination environments of Bi in Bi2S3 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 Cu4Bi5S10, whereas Bi s–p hybridization coexists with a much reduced lone pair in Bi2S3 at high pressure.

U2 - 10.1016/j.jssc.2010.07.022

DO - 10.1016/j.jssc.2010.07.022

M3 - Journal article

VL - 183

SP - 2133

EP - 2143

JO - Journal of Solid State Chemistry

JF - Journal of Solid State Chemistry

SN - 0022-4596

IS - 9

ER -

ID: 32436528