High-pressure phase transitions and compressibility of wolframite-type tungstates

TL;DR

This study investigates the high-pressure phase transitions and compressibility of wolframite-type tungstates using experimental x-ray techniques and ab initio calculations, revealing multiple phase transitions and detailed atomic compression behaviors.

Contribution

It provides new experimental and theoretical insights into the phase diagram and compressibility of wolframite-type tungstates under high pressure, including transition pressures and atomic structure changes.

Findings

MgWO4 undergoes two phase transitions at 17.1 and 31 GPa.

ZnWO4 transitions at 15.1 GPa, with additional transitions predicted at higher pressures.

The low-pressure phase's equation of state and atomic compression details are characterized.

Abstract

This paper reports an investigation on the phase diagram and compressibility of wolframite-type tungstates by means of x-ray powder diffraction and absorption in a diamond-anvil cell and ab initio calculations. The diffraction experiments show that monoclinic wolframite-type MgWO4 suffers at least two phase transitions, the first one being to a triclinic polymorph with a structure similar to that of CuWO4 and FeMoO4-II. The onset of each transition is detected at 17.1 and 31 GPa. In ZnWO4 the onset of the monoclinic-triclinic transition has been also found at 15.1 GPa. These findings are supported by density-functional theory calculations, which predict the occurrence of additional transitions upon further compression. Calculations have been also performed for wolframite-type MnWO4, which is found to have an antiferromagnetic configuration. In addition, x-ray absorption and diffraction experiments as well as calculations reveal details of the local-atomic compression in the studied compounds. In particular, below the transition pressure the ZnO6 and equivalent polyhedra tend to become more regular, whereas the WO6 octahedra remain almost unchanged. Fitting the pressure-volume data we obtained the equation of state for the low-pressure phase of MgWO4 and ZnWO4. These and previous results on MnWO4 and CdWO4 are compared with the calculations, being the compressibility of wolframite-type tungstates systematically discussed. Finally Raman spectroscopy measurements and lattice dynamics calculations are presented for MgWO4.