  We performed high-pressure angle dispersive x-ray diffraction measurements on
Fe5Si3 and Ni2Si up to 75 GPa. Both materials were synthesized in bulk
quantities via a solid-state reaction. In the pressure range covered by the
experiments, no evidence of the occurrence of phase transitions was observed.
On top of that, Fe5Si3 was found to compress isotropically, whereas an
anisotropic compression was observed in Ni2Si. The linear incompressibility of
Ni2Si along the c-axis is similar in magnitude to the linear incompressibility
of diamond. This fact is related to the higher valence-electron charge density
of Ni2Si along the c-axis. The observed anisotropic compression of Ni2Si is
also related to the layered structure of Ni2Si where hexagonal layers of Ni2+
cations alternate with graphite-like layers formed by (NiSi)2- entities. The
experimental results are supported by ab initio total-energy calculations
carried out using density functional theory and the pseudopotential method. For
Fe5Si3, the calculations also predicted a phase transition at 283 GPa from the
hexagonal P63/mcm phase to the cubic structure adopted by Fe and Si in the
garnet Fe5Si3O12. The room-temperature equations of state for Fe5Si3 and Ni2Si
are also reported and a possible correlation between the bulk modulus of iron
silicides and the coordination number of their minority element is discussed.
Finally, we report novel descriptions of these structures, in particular of the
predicted high-pressure phase of Fe5Si3 (the cation subarray in the garnet
Fe5Si3O12), which can be derived from spinel Fe2SiO4 (Fe6Si3O12).
