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Unveiling the role of the lone electron pair in sesquioxides at high pressure: compressibility of β-Sb2O3

DOI: 10.1039/D1DT00268F DOI Help

Authors: Juan Angel Sans (Universitat Politècnica de València) , Francisco Javier Manjon (Universitat Politècnica de València) , André Luis De Jesus Pereira (Universidad Politécnica de Valencia; nstituto Tecnológico de Aeronáutica (ITA)) , Javier Ruiz-Fuertes (Universidad de Cantabria) , Catalin Popescu (ALBA-CELLS) , Alfonso Muñoz (Universidad de La Laguna) , Plácida Rodríguez-Hernández (Universidad de La Laguna) , Julio Pellicer-Porres (Universitat de València) , Vanesa Paula Cuenca-Gotor (Universitat Politècnica de València) , Julia Contreras-Garcia (CNRS, UMR 7616) , Jordi Ibañez (Geosciences Barcelona (GEO3BCN-CSIC)) , Virginia Monteseguro (Universidad de Cantabria; Universitat de València)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Dalton Transactions , VOL 854

State: Published (Approved)
Published: March 2021
Diamond Proposal Number(s): 22223

Abstract: The structural, vibrational and electronic properties of the compressed β-Sb2O3 polymorph, a.k.a. mineral valentinite, have been investigated in a joint experimental and theoretical study up to 23 GPa. The compressibility of the lattice parameters, unit-cell volume and polyhedral unit volume as well as the behaviour of its Raman- and IR-active modes under compression have been interpreted on the basis of ab initio theoretical simulations. Valentinite shows an unusual compressibility up to 15 GPa with four different pressure ranges, whose critical pressures are 2, 4, and 10 GPa. The pressure dependence of the main structural units, the lack of soft phonons, and the electronic density charge topology address the changes at those critical pressures to isostructural phase transitions of degree higher than 2. In particular, the transitions at 2 and 4 GPa can be ascribed to the changes in the interaction between the stereochemically-active lone electron pairs of Sb atoms under compression. The changes observed above 10 GPa, characterized by a general softening of several Raman- and IR-active modes, point to a structural instability prior to the 1st-order transition occurring above 15 GPa. Above this pressure, a tentative new high-pressure phase (s.g. Pcc2) has been assigned by single-crystal and powder X-ray diffraction measurements.

Subject Areas: Materials, Chemistry

Instruments: I19-Small Molecule Single Crystal Diffraction

Other Facilities: BL04-MSPD at ALBA

Discipline Tags:

Material Sciences Chemistry

Technical Tags:

Diffraction Single Crystal X-ray Diffraction (SXRD)