Freezing in Resonance Structures for Better Packing: XeF2 Becomes (XeF+)(F−) at Large Compression

Recent high-pressure experiments conducted on xenon difluoride (XeF2) suggested that this compound undergoes several phase transitions up to 100 GPa, becoming metallic above 70 GPa. In this theoretical study, in contrast to experiment, we find that the ambient pressure molecular structure of xenon difluoride, of I4/mmm symmetry, remains the most stable one up to 105 GPa. In our computations, the structures suggested from experiment have either much higher enthalpies than the I4/mmm structure or converge to that structure upon geometry optimization. We discuss these discrepancies between experiment and calculation and point to an alternative interpretation of the measured cell vectors of XeF2 at high pressure. At pressures exceeding those studied experimentally, above 105 GPa, the I4/mmm structure transforms to one of Pnma symmetry. The Pnma phase contains bent FXeF molecules, with unequal Xe−F distances, and begins to bring other fluorines into the coordination sphere of the Xe. Further compression of this structure up to 200 GPa essentially results in self-dissociation of XeF2 into an ionic solid (i.e., [XeF]+F−), similar to what is observed for nitrous oxide (N2O) at high pressure.