Pressure-Driven Symmetry-Preserving Phase Transitions in Co(IO3)(2)

Abstract

[EN] High-pressure synchrotron X-ray diffraction studies of cobalt iodate, Co(IO3)(2), reveal a counterintuitive pressure-induced expansion along certain crystallographic directions. High-pressure Raman and infrared spectroscopy, combined with density-functional theory calculations, reveal that with increasing pressure, it becomes energetically favorable for certain I-O bonds to increase in length over the full range of pressure studied up to 28 GPa. This phenomenon is driven by the high-pressure behavior of iodate ion lone electron pairs. Two pressure-induced isosymmetric monoclinic-monoclinic phase transitions are observed at around 3.0 and 9.0 GPa, which are characterized by increasing oxygen coordination of the iodine atoms and the probable formation of pressure-induced metavalent bonds. Pressure-volume equations of state are presented, as well as a detailed discussion of the pressure dependences of the observed Raman- and infrared-active modes, which clarifies previous inconsistencies in the literature.