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Preferred ion diffusion pathways and activation energies for Ag in the crystal structure of stephanite, Ag5SbS4

Published online by Cambridge University Press:  05 July 2018

M. Leitl ,
A. Pfitzner  and
L. Bindi
M. Leitl
Affiliation:
BASF Construction Chemicals GmbH, Dr.-Albert-Frank-Straße 32, D-83308 Trostberg, Germany Institut für Anorganische Chemie, Universität Regensburg, Universitätsstrasse 31, D-93040, Regensburg, Germany
A. Pfitzner
Affiliation:
Institut für Anorganische Chemie, Universität Regensburg, Universitätsstrasse 31, D-93040, Regensburg, Germany
L. Bindi*
Affiliation:
Museo di Storia Naturale, Sezione di Mineralogia, Università degli Studi di Firenze, Via La Pira, 4, I-50121, Firenze, Italy
*
* E-mail: [email protected]
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Abstract

The crystal structure of stephanite fromthe type locality, Freiberg District, Saxony, Germany, was refined in the space group Cmc21, up to a final R index of 0.0427. Unit-cell parameters are: a 7.8329(6) Å, b 12.458(1) Å, c 8.5272(7) Å, V 832.1(1) Å3; Z = 4. The previously reported structural model is confirmed, but a higher-precision refinement was achieved herein by the introduction of thirdorder non-harmonic Gram-Charlier tensors for one Ag atom. In the structure of stephanite, Sb forms isolated SbS3 pyramids, which typically occur in sulphosalts, and Ag occupies sites with coordination ranging fromtriangular to almost tetrahedral. Both the Sb–S and Ag–S bond distances closely match the values commonly observed in the structures of other Ag sulphosalts and sulphides.

The use of non-harmonic parameters for Ag allowed a better description of the electron density related to Ag, which is usually difficult to refine in good ionic conductors. A careful analysis of the energy barriers between the Ag sites defines preferred ion-diffusion pathways within the crystal structure of stephanite. The diffusion of Ag ions occurs preferentially along the sites Ag1 and Ag2, giving rise to two-dimensional nets of Ag atoms in which the ion conduction probably takes place.

Keywords

stephanitecrystal-structure refinementnon-harmonic approachAgdiffusion pathwayionic conductivity.
Type
Research Article
Information
Mineralogical Magazine , Volume 73 , Issue 1 , February 2009 , pp. 17 - 26
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2009

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