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Vibrations and Phase Stability in Mixed Valence Antimony Oxide

Cite this: Inorg. Chem. 2023, 62, 40, 16464–16474
Publication Date (Web):September 25, 2023
https://doi.org/10.1021/acs.inorgchem.3c02189
Copyright © 2023 American Chemical Society

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    Abstract

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    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 stability and lower symmetry despite being in the high-temperature phase. Since the vibrational entropy difference is small, it is unlikely to stabilize the α phase. Our results suggest that the α phase is more stable only because the material is not fully stoichiometric.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.inorgchem.3c02189.

    • Powder X-ray and neutron diffraction data, additional Mössbauer spectroscopy parameters, TGA results, energy vs COHP, supercells used for defect calculations, experimental and calculated NIS spectra, specific heat (CV) information, electronic DOS, calculated phonon dispersions, comparisons of different functionals used for DFT phonon calculations, neutron-weighted calculated DPS, comparison of experimental INS spectra and calculated INS spectra between both phases, ICOHP contributions to band structure energies, experimental and DFT calculated lattice constants and angles, and calculated modes for each phase (PDF)

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