Thorite versus huttonite: stability, electronic properties and X-ray emission spectra from first-principle calculations

The structural, electronic properties and stability of thorium orthosilicate ThSiO₄ polymorphs: thorite and huttonite are investigated by means of the full-potential linearized augmented-plane-wave method with the generalized gradient approximation for the exchange-correlation potential (FLAPW-GGA). The forbidden gaps of thorite and huttonite are estimated at about 7.8 and 7.6 eV, respectively. It is found that Th5f states in ThSiO₄ partially overlap with occupied O2p bands. The data obtained showed that thorite is more stable than huttonite; in turn both ThSiO₄ polymorphs are unstable with respect to their constituent binary oxides (thorianite ThO₂ and α-quartz SiO₂) in agreement with the experiments. The theoretical shapes of X-ray emission (XES) (Si,O)Kα,β spectra for thorite, huttonite as well as for SiO₂ and ThO₂ are calculated and discussed. We show that the XES spectroscopy near the (Si,O)K edge may be very useful technique not only for detailed investigation of the bulk-electronic structure of Th silicates but also for the phase analysis of complex mineral samples containing these species.