A novel approach to the structural distortions of U/Th snub-disphenoids and their control on zircon → reidite type phase transitions of U1-x Th x SiO4.

Coffinite (USiO4) and thorite (ThSiO4) are conspicuous radiogenic silicates in the geonomy. They form U1-x Th x SiO4 (uranothorite) solid solutions in zircon-type phase. Investigating the phase-evolution of these minerals is of utmost significance in realizing their applicability in the front-as well as at the back-end of nuclear industries. We carried out a systematic study of zircon- to reidite-type (tetragonal I41/amd to I41/a) structural transitions of U1-x Th x SiO4 solid solution, and investigated their mechanical behaviour. We found a unique behaviour of transition pressure with the change in U-Th concentration in the solid solution. The phase transition pressure (p t) is found to be minimum for x = 0.5. We develop the necessary formalism and present an efficient method to estimate the longitudinal and angular distortions of U/ThO8-triangular dodecahedra (snub-disphenoids). We have parameterized two new factors: δ (longitudinal distortions) and σ 2 (angular distortions) to quantify the polyhedral distortions. A detailed analysis of U/ThO8 snub-disphenoidal distortions is presented to address such variation of p t with U and Th concentration. We argue that our approach is independent of polyhedral volume and can be used for any AB8 (A: cation, B: anion) type snub-disphenoidal system.

Electronic structure, optical properties and the mechanism of the B3-B8 phase transition of BeSe: insights from hybrid functionals, lattice dynamics and NPH molecular dynamics.

We have investigated the electronic structure and the mechanism of the pressure induced phase transition of beryllium selenide (BeSe) by employing a first-principles pseudopotential method within the framework of density functional theory. Our study demonstrates that use of the hybrid PBE0 functional (PBE stands for Perdew, Burke and Ernzerhof) leads to significant improvement in the band gap calculations, compared to those using either of the common density functionals (local density approximation (LDA) and generalized gradient approximation (GGA)), which severely underestimate the band gap of BeSe. The band gap obtained from the hybrid PBE0 functional shows excellent agreement with available experimental data. A constant-pressure (NPH) first-principles molecular dynamics (FPMD) approach has been adopted to characterize the first-order pressure induced phase transition from the zinc blende (ZB) to the nickel arsenide (NiAs) structure. We have shown that the FPMD simulation overestimates the transition pressure P(T) (compared to static enthalpy and experimental data) due to overpressure in the simulation box. The MD simulation reveals the structural pathway (cubic → orthorhombic → monoclinic → hexagonal), leading from the ZB phase to the NiAs phase. To find an explanation for the phase transition we calculated the vibrational and elastic properties under pressure. Negative Grüneisen parameters were obtained for the transverse acoustic phonon modes at the X and L high symmetry points. However, no mechanical instability or imaginary frequencies were found at pressures near P(T). Thus the transition results from a thermodynamic instability rather than an elastic/dynamical one. We have also calculated the optical properties of both the B3 and B8 phases, such as the real and imaginary parts of the dielectric constant, reflectivity, loss function and refractive index, and compared them with the existing experimental and theoretical data. An abrupt decrease is obtained from the reflectivity spectrum of the NiAs phase at P(T), which is supported from the peaks in the loss function.