Estrutura e propriedades elásticas das fases alpha e gama do ZrW2O8

Abstract

The crystalline structure and some elastic properties of the a and g phases of zirconium tungstate, ZrW2O8, were calculated according to Density Functional Theory using the B3LYP functional (DFT/B3LYP). The structure of a-ZrW2O8, was optimized at different pressures and its elastic constants were estimates. The interatomic iterations, ranked in terms of bond compressibilities, decrease according to the sequence W-O > Zr· · ·W > Zr-O. The tetrahedra around tungsten atoms are found to be much stiffer than the ZrO6 octahedra. These latter are, in fact, more compressible than the a-ZrW2O8 unit cell. The elastic constants calculated in the athermal limit are in excellent agreement with recent experimental results obtained near 0 K. The compression mechanism around W1 and W2 atoms is quite different. While the former can be described essentially in terms of a correlated polyhedral rotation, the latter involves correlated rotation of the first coordination polyhedra and translation of WO4 units downward along the < 111> axis. As far as these modes of deformation should bear some resemblance to the low-energy modes responsible for the negative thermal expansion in zirconium tungstate, this result can shed some light on the microscopic mechanism behind this phenomenon. The structure of g-ZrW2O8 was optimized at ambient pressure and for V/V0 = 0.97 (threshold of the g ® amorphous phase transition) aiming to study the evolution of the structure of this phase with the pressure and the pressure induced amorphization mechanism. A reduction of 3 % in the volume of the unit cell leads to a variation greater than 1,5 % in the interatomic distances between the terminal atoms and the tungsten of the nearest tetrahedron. Therefore, it is expected that the reduction of 15 % in the molar volume with the g ® amorphous transition promotes the formation of new W-O bonds, which would be responsible for the metaestable retention of the amorphous phase upon pressure release.