The influence of channel anion identity on the high-pressure crystal structure, compressibility, and stability of apatite

The material properties of the common phosphate mineral apatite are influenced by the identity of the channel anion, which

is usually F−, Cl−, or (OH)−. Density functional theory calculations have been used to determine the effect of channel anion

identity on the compressibility and structure of apatite. Hydroxyapatite and fluorapatite are found to have similar zero pressure

bulk moduli, of 79.2 and 82.1 GPa, respectively, while chlorapatite is considerably more compressible, with K₀=55.0

GPa. While the space groups of hydroxyapatite and fluorapatite do not change between 0 and 25 GPa, symmetrization of

the Cl− site in chlorapatite at ~7.5 GPa causes the space group to change from P2₁/b to P6₃/m. Examination of the valence

electron density distribution in chlorapatite reveals that this symmetry change is associated with a change in the coordination

of the Cl− anion from threefold to sixfold coordinated by Ca. We also calculate the pressure at which apatite decomposes to

form tuite, a calcium orthophosphate mineral, and find that the transition pressure is sensitive to the identity of the channel

anion, being lowest for fluorapatite (13.8 GPa) and highest for chlorapatite (26.9 GPa). Calculations are also performed

within the DFT-D2 framework to investigate the influence of dispersion forces on the compressibility of apatite minerals.