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A note on the bonding,optical spectrum and composition of tetrahedrite
Authors:Raymond Jeanloz  Mary L Johnson
Institution:1. Department of Geology and Geophysics, University of California, 94720, Berkeley, California, USA
2. Department of Chemistry and Biochemistry, University of California, 90024, Los Angeles, California, USA
Abstract:Tetrahedrites of composition (Cu, Ag)10(Cu2, Fe, Zn)2(Sb, As)4S13 or Cu12Sb14/3S13 have 208 valence electrons per unit cell and are expected to be semiconductors. The bands are full in these cases, whereas compositions towards the classical formula Cu12Sb4S13 (204 valence electrons per unit cell) have only partially filled bands and are therefore expected to be metallic. These predictions are supported by new optical absorption spectra of tetrahedrites with 205 and 208 valence electrons per unit cell. The gap between valence and conduction bands of the semiconductor is about 1.7 (±0.2) eV. A further prediction based on a nearly-free electron model is that 208 valence electrons per unit cell represent a compositional limit for tetrahedrites, and that the stability increases as compositions approach this limit. Existing data indicate an exponential increase in the number of occurrences as the limit is approached.
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