Full crystal structure, hydrogen bonding and spectroscopic, mechanical and thermodynamic properties of mineral...

The determination of the full crystal structure of the uranyl sulfate mineral uranopilite, (UO₂)₆(SO₄)O₂(OH)₆·14H₂O, including the positions of the hydrogen atoms within the corresponding unit cell, has not been feasible to date due to the poor quality of its X-ray diffraction pattern. In this paper, the complete crystal structure of uranopilite is established for the first time by means of first principles solid-state calculations based in density functional theory employing a large plane wave basis set and pseudopotential functions. The computed unit-cell parameters and structural data for the non-hydrogen atoms are in excellent agreement with the available experimental data. The computed X-ray diffraction pattern is also in satisfactory agreement with the experimental pattern. The infrared spectrum of uranopilite is collected from a natural crystal specimen originating in Jáchymov (Czech Republic) and computed employing density functional perturbation theory. The theoretical and experimental vibrational spectra are highly consistent. Therefore, a full assignment of the bands in the experimental infrared spectrum is performed using a normal mode analysis of the first principles vibrational results. One overtone and six combination bands are recognized in the infrared spectrum. The elasticity tensor and phonon spectra of uranopilite are computed from the optimized crystal structure and used to analyze its mechanical stability, to obtain a rich set of elastic properties and to derive its fundamental thermodynamic properties as a function of temperature. Uranopilite is shown to have a large mechanical anisotropy and to exhibit the negative Poisson's ratio and negative linear compressibility phenomena. The calculated specific heat and entropy at 298.15 K are 179.6 and 209.0 J K^-1 mol^-1, respectively. The computed fundamental thermodynamic functions of uranopilite are employed to obtain its thermodynamic functions of formation in terms of the elements and the thermodynamic properties of a set of chemical reactions relating uranopilite with a representative group of secondary phases of spent nuclear fuel. From the reaction thermodynamic data, the relative stability of uranopilite with respect to these secondary phases is evaluated as a function of temperature and under different hydrogen peroxide concentrations. From the results, it follows that uranopilite has a very large thermodynamic stability in the presence of hydrogen peroxide. The high stability of uranopilite under this condition justify its early crystallization in the paragenetic sequence of secondary phases occurring when uranium dioxide is exposed to sulfur-rich solutions.