Persistence of the stereochemical activity of the Bi3+lone electron pair in Bi2Ga4O9up to 50 GPa and crystal structure of the high-pressure phase

Abstract

The crystal structure of the high-pressure phase of bismuth gallium oxide, Bi2Ga4O9, was determined up to 30.5 (5) GPa fromin situsingle-crystal in-house and synchrotron X-ray diffraction. Structures were refined at ambient conditions and at pressures of 3.3 (2), 6.2 (3), 8.9 (1) and 14.9 (3) GPa for the low-pressure phase, and at 21.4 (5) and 30.5 (5) GPa for the high-pressure phase. The mode-Grüneisen parameters for the Raman modes of the low-pressure structure and the changes of the modes induced by the phase transition were obtained from Raman spectroscopic measurements. Complementary quantum-mechanical calculations based on density-functional theory were performed between 0 and 50 GPa. The phase transition is driven by a large spontaneous displacement of one O atom from a fully constrained position. The density-functional theory (DFT) model confirmed the persistence of the stereochemical activity of the lone electron pair up to at least 50 GPa in accordance with the crystal structure of the high-pressure phase. While the stereochemcial activity of the lone electron pair of Bi^{3+} is reduced at increasing pressure, a symmetrization of the bismuth coordination was not observed in this pressure range. This shows an unexpected stability of the localization of the lone electron pair and of its stereochemical activity at high pressure.