Raman spectroscopic study of the mineral gerstleyite Na₂(Sb,As)₈S₁₃·2H₂O and comparison with some heavy‐metal sulfides

Abstract

The mineral gerstleyite is described as a sulfosalt as opposed to a sulfide. This study focuses on the Raman spectrum of gerstleyite Na 2 (Sb,As) 8 S 13 ·2H 2 O and makes a comparison with the Raman spectra of other common sulfides including stibnite, cinnabar and realgar. The intense Raman bands of gerstleyite at 286 and 308 cm −1 are assigned to the SbS 3 E antisymmetric and A 1 symmetric stretching modes of the SbS 3 units. The band at 251 cm −1 is assigned to the bending mode of the SbS 3 units. The mineral stibnite also has basic structural units of Sb 2 S 3 and SbS 3 pyramids with C 3v symmetry. Raman bands of stibnite Sb 2 S 3 at 250, 296, 372 and 448 cm −1 are assigned to Sb-S stretching vibrations and the bands at 145 and 188 cm −1 to S-Sb-S bending modes. The Raman band for cinnabar HgS at 253 cm −1 fits well with the assignment of the band for gerstleyite at 251 cm −1 to the S-Sb-S bending mode. Raman bands in similar positions are observed for realgar AsS and orpiment As 2 S 3 .

Sulfur-Vacancy Passivation in Solution-Processed Sb2S3 Thin Films: Influence on Photovoltaic Interfaces

“…In addition, the weak bands at 126 and 155 cm –1 can be attributed to A g and B 1g modes of vibration, respectively. The Raman shifts obtained from our measurements are in agreement with the reported values . The spectra are mostly dominated by Raman modes at 281.5 and 309.5 cm –1 corresponding to antisymmetric and symmetric Sb–S stretching vibrations in Sb 2 S 3 , respectively.…”

“…A closer inspection of the modes showed that under the influence of precursor stoichiometry, the intensity of the modes changed; the peak corresponding to symmetric stretching gained its intensity with increasing sulfur content in Sb 2 S 3 (less sulfur vacancies) at the cost of the asymmetric stretching mode. Such a change in the peak intensity has also been explained to be due to the absence of sulfur vacancies leading to shorter Sb–S bonds and vice versa …”

Gungerite, TlAs5Sb4S13, a new thallium sulfosalt with a complex structure containing covalent As-As bonds

“…An additional band observed in the Raman spectra of stibnite (in the range 251-236 cm -1 ) conforms to the shoulder at 240 cm -1 in the spectrum of gungerite. This band was assigned to the bending mode of the SbS 3 units (Frost et al 2010).…”

Mineralogy of the Vorontsovskoe gold deposit (Northern Urals). Part 3: sulfosalts

“…3г) волновые числа в интервале 280-370 см -1 относятся к As-S валентным колебаниям. Сильная полоса при 294 см -1 с плечом при 240 см -1 соответствует деформационной моде группы SbS 3 (Frost et al, 2010). Полосы в диапазоне 302-310 см -1 отнесены к антисимметричной, а полоса при 334 см -1 -к симметричной валентной моде SbS 3 , слабые полосы при 282 и 270 см -1 -соответственно, к симметричной и антисимметричной деформационной моде SbS 3 (Kharbish et al, 2009).…”