Abstract: An experimental and theoretical study of the structural properties of monoclinic bismuth oxide (α-Bi2O3) under high pressures is here reported. Both synthetic and mineral bismite powder samples have been compressed up to 45 GPa and their equations of state have been determined with angle-dispersive x-ray diffraction measurements. Experimental results have been also compared with theoretical calculations which suggest the possibility of several phase transitions below 10 GPa. However, experiments reveal only a pressure-induced amorphization between 15 and 25 GPa, depending on sample quality and deviatoric stresses. The amorphous phase has been followed up to 45 GPa and its nature discussed. ; Financial support from the Spanish Consolider Ingenio 2010 Program (MALTA Project No. CSD2007-00045) is acknowledged. This work was also supported by Brazilian Conselho Nacional de Desenvolvimento Científico e Tecnoloógico (CNPq) under project 201050/2012-9, Spanish MICINN under projects MAT2010-21270-C04-01/03/04, Spanish MINECO under project CTQ2012-36253-C03-02, by Generalitat Valenciana through project GVA-ACOMP- 2013-012 and from Vicerrectorado de Investigación de la Universitat Politècnica de València under projects UPV2011-0914 PAID-05-11 and UPV2011-0966 PAID-06- 11. Supercomputer time has been provided by the Red Española de Supercomputacioón (RES) and the MALTA cluster.
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