Authors
Duncan H Moseley, Rinkle Juneja, Luke L Daemen, Ilya Sergueev, René Steinbrügge, Olaf Leupold, Yongqiang Cheng, Valentino R Cooper, Lucas Lindsay, Michelle K Kidder, Michael E Manley, Raphaël P Hermann
Publication date
2023/9/25
Journal
Inorganic Chemistry
Volume
62
Issue
40
Pages
16464-16474
Publisher
American Chemical Society
Description
α-Sb2O4 (cervantite) and β-Sb2O4 (clinocervantite) are mixed valence compounds with equal proportions of SbIII and SbV as represented in the formula SbIIISbVO4. Their structure and properties can be difficult to calculate owing to the SbIII lone-pair electrons. Here, we present a study of the lattice dynamics and vibrational properties using a combination of inelastic neutron scattering, Mössbauer spectroscopy, nuclear inelastic scattering, and density functional theory (DFT) calculations. DFT calculations that account for lone-pair electrons match the experimental densities of phonon states. Mössbauer spectroscopy reveals the β phase to be significantly harder than the α phase. Calculations with O vacancies reveal the possibility for nonstoichiometric proportions of SbIII and SbV in both phases. An open question is what drives the stability of the α phase over the β phase, as the latter shows pronounced kinetic …
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Scholar articles
DH Moseley, R Juneja, LL Daemen, I Sergueev… - Inorganic Chemistry, 2023