High-Pressure X-Ray Diffraction Study of Scheelite-type Perrhenates

TL;DR

This study investigates how pressure affects the crystal structure of scheelite-type perrhenates using X-ray diffraction and density-functional theory, revealing phase transitions and elastic properties.

Contribution

It provides new experimental and theoretical insights into pressure-induced phase transitions and elastic properties of AgReO4, KReO4, and RbReO4 perrhenates.

Findings

Observed scheelite-to-fergusonite phase transitions at specific pressures.

Determined pressure-volume equations of state for the compounds.

Density-functional theory accurately describes low-pressure phases but not phase transitions.

Abstract

The effects of pressure on the crystal structure of scheelite-type perrhenates were studied using synchrotron powder X-ray diffraction and density-functional theory. At ambient conditions, the studied materials AgReO4, KReO4, and RbReO4, exhibit a tetragonal scheelite-type crystal structure described by space group I41/a. Under compression, a transition from scheelite-to-M${\prime}$-fergusonite (space group P21/c) was observed at 1.6 and 7.4 GPa for RbReO4 and KReO4, respectively. The transition involves a relative volume decrease. On the other hand, AgReO4 underwent a phase transition to the M-fergusonite structure (space group I2/a) at 13.6 GPa. In this case there is no appreciable volume discontinuity. The room-temperature pressure-volume equation of state for the three studied perrhenates was estimated using a second-order Birch-Murnaghan equation of state. The results for the low-pressure phase are confirmed by density-functional theory calculations. The analysis of the bulk modulus shows that the compressibility of the compounds decreases following the sequence RbReO4 > KReO4 > AgReO4, which is related to the compressibility of the RbO8, KO8, and AgO8 bidisphenoid units. Density-functional theory also offers valuable insights into the elastic constants. Despite giving a good description for the low-pressure phase in the three compounds, density-functional theory cannot catch the structural phase transition observed in experiments. Reasons for it are discussed in the manuscript.