A novel approach to quantify the structural distortions of U/Th snub-disphenoids and their role in zircon to reidite type phase transitions of uranothorite

TL;DR

This study uses density functional theory to link Th/(U+Th) ratio with pressure-induced phase transitions in uranothorite, introducing a new method to quantify distortions in U/Th polyhedra and explaining transition behavior.

Contribution

It presents a novel approach to quantify U/Th polyhedral distortions and correlates these with phase transition pressures in uranothorite, revealing a minimum at equal U and Th content.

Findings

Transition pressure is minimized at Th/(U+Th)=0.5.

Polyhedral bond angle distortions are minimized at Th/(U+Th)=0.5.

Zircon phase shows minimum compressibility at equal U and Th content.

Abstract

Our density functional study reveals a peculiar relation between the normalized Th content i.e. Th/(U+Th) and the hydrostatic pressure enforcing zircon to reidite type transition in uranothorite solid solution. We found that the transition pressure exhibits a minimum when Th/(U+Th) = 0.50 i.e. when the unit cell contains equal amount of U and Th. Any change in normalized Th content, as we move towards the U and Th end-members of the series, shows a significant jump in zircon-reidite transition pressure. In order to explain this behavior, we proposed a novel method of quantifying the distortions of U/Th-coordination polyhedra which manifest themselves as a triangular dodecahedron or snub-disphenoid. We have theoretically defined two parameters: one related to the two geometrically different U/Th-O bond lengths, having a fixed ratio between them for regular triangular dodecahedra irrespective of the volume and the other with three kinds of O-U-O and O-Th-O bond angles with multiplicities of 2, 4 and 12, respectively. The bond angle distortion for both U and Th-polyhedra were found to show a maximum in zircon phase and a minimum in reidite phase corresponding to Th/(U+Th) = 0.5. Since, the difference in angular distortion is minimum in case of Th/(U+Th) = 0.5, a lesser hydrostatic pressure is capable of triggering the transition, compared to the other members of this series. The bond length distortion is also characterized by a maximum in the reidite phase at the equal concentration of U and Th. Our finding is also complemented by the minimum compressibility observed in the zircon phase when the atomic percentage of U and Th are equal.