Density functional theory demonstrates orientation effects in the Raman spectra of hydroxy‐ and carbonated apatite

Raman spectroscopy is widely used to examine the carbonate content within bone apatite, but Raman spectra are also sensitive to orientation effects between the polarisation of the incoming laser light and the sample orientation. This may lead to discrepancies when using Raman spectroscopy to evaluate the carbonate content as the extent of crystal organisation can change depending on the type of bone, age, and presence of mineralisation disorders in the organism. It is experimentally very challenging to evaluate the effect of orientation using individual bone crystals. Therefore, we have used density functional theory to examine the effect of orientation in apatitic materials. We examined hydroxyapatite and three different types of carbonated apatite: A-type where the carbonate ion substitutes the two OH groups in the unit cell, B-type where co-substitution occurs between carbonate in a phosphate position and Na+ for Ca2+ to maintain charge balance, and AB-type where carbonate sits in both A-site and B-site. Our simulations show that the OH group in hydroxyapatite has a strong orientation dependence, consistent with previous literature. In addition, the phosphate and carbonate bands of the apatitic structures are predicted to be orientation dependent, where the maximum scattering efficiency occurs in configurations in which the laser polarisation is parallel to the crystallographic axes of the material. The intensity changes of the phosphate and carbonate bands are not consistent upon changing orientations and thus may lead to an underestimation of carbonate contents if insufficient sampling points are used during bone analysis.