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Article

Antimony-121 Mössbauer Spectral Study of α-Zn₄Sb₃

Raphaël P. Hermann and Fernande Grandjean

Department of Physics, B5, University of Lige, B-4000 Sart-Tilman, Belgium

Tsi-Chi Chen, Dennis E. Brown, and C. E. Johnson

Department of Physics, Northern Illinois University, De Kalb, Illinois 60115

G. Jeffrey Snyder

Department of Materials Science, California Institute of Technology, 1200 East California Boulevard, Pasadena, California 91125

Gary J. Long*

Department of Chemistry, University of MissouriRolla, Rolla, Missouri 65409-0010

Inorg. Chem., 2007, 46 (3), pp 767–770

DOI: 10.1021/ic061533x

Publication Date (Web): January 5, 2007

To whom correspondence should be addressed. E-mail: glong@umr.edu.

Abstract

The Mössbauer spectra of α-Zn₄Sb₃, a compound that is best formulated as α-Zn₁₃Sb₁₀ or (Zn²⁺)₁₃(Sb³^-)₆(Sb₂⁴^-)₂, have been measured between 5 and 120 K. The resulting six spectra have been simultaneously fit with two components in the ratio of 3:2 corresponding to the Sb³^- and Sb²^- ions identified in this valence semiconductor. The fits yield temperature independent isomer shifts of −8.17(2) and −9.73(2) mm/s and quadrupole interactions of −4.9(2) and 0 mm/s for the Sb³^- and Sb²^- ions, respectively; the corresponding Mössbauer temperatures are 197(5) and 207(5) K, temperatures that are lower than the Debye temperature of β-Zn₄Sb₃. The isomer shifts correspond to electronic configurations between 5s²5p⁶ and 5s^1.755p^4.01 for the Sb³^- ions and between 5s²5p⁵ and 5s^1.805p^3.38 for the Sb²^- ions, configurations that are in good agreement with the expected configurations for this valence semiconductor and with the results of band structure calculations.