Incommensurate atomic density waves in the high-pressure IVb phase of barium

The host–guest structures of elements at high pressure discovered a decade ago still leave many open questions due to the lack of precise models based on full exploitation of the diffraction data. This concerns in particular Ba IV, which is stable in the range 12–45 GPa. With the example of phase Ba IVb, which is characterized here for the first time, a systematic analysis is presented of possible host–guest structure models based on high-quality single-crystal diffraction data obtained with synchrotron radiation at six different pressures between 16.5 and 19.6 GPa. It is shown that a new incommensurately modulated (IM) structure model better fits the experimental data. Unlike the composite models which are commonly reported for the Ba IV phases, the IM model reveals a density wave and its pressure-dependent evolution. The crucial role played by the selected model in the interpretation of structure evolution under pressure is discussed. The findings give a new experimental basis for a better understanding of the nature of host–guest structures.