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High-Pressure Phase Transitions of Zinc Difluoride up to 55 GPa
Dominik Kurzydłowski1, Anna Oleksiak1, Sharad Babu Pillai2
1Faculty of Mathematics and Natural Sciences , Cardinal Stefan Wyszyński University , Warsaw 01-038 , Poland.
Abstract:
Studying the effect of high pressure (exceeding 10 kbar) on the structure of solids allows us to gain deeper insight into the mechanism governing crystal structure stability. Here, we report a study on the high-pressure behavior of zinc difluoride (ZnF2)-an archetypical ionic compound which at ambient pressure adopts the rutile (TiO2) structure. Previous investigations, limited to a pressure of 15 GPa, revealed that this compound undergoes two pressure-induced phase transitions, i.e., TiO2 → CaCl2 at 4.5 GPa and CaCl2 → HP-PdF2 at 10 GPa. Within this joint experimental-theoretical study, we extend the room-temperature phase diagram of ZnF2 up to 55 GPa. By means of Raman spectroscopy measurements we identify two new phase transitions, HP-PdF2 → HP1-AgF2 at 30 GPa and HP1-AgF2 → PbCl2 at 44 GPa. These results are confirmed by density functional theory calculations which indicate that in the HP1-AgF2 polymorph the coordination sphere of Zn2+ undergoes drastic changes upon compression. Our results point to important differences in the high-pressure behavior of ZnF2 and MgF2, despite the fact that both compounds contain cations of similar size. We also argue that the HP1-AgF2 structure, previously observed only for AgF2, might be observed at large compression in other AB2 compounds.
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