The trisulfur radical ion S3•- controls platinum transport by hydrothermal fluids.

Platinum group elements (PGE) are considered to be very poorly soluble in aqueous fluids in most natural hydrothermal-magmatic contexts and industrial processes. Here, we combined in situ X-ray absorption spectroscopy and solubility experiments with atomistic and thermodynamic simulations to demonstrate that the trisulfur radical ion S3•- forms very stable and soluble complexes with both PtII and PtIV in sulfur-bearing aqueous solution at elevated temperatures (∼300 °C). These Pt-bearing species enable (re)mobilization, transfer, and focused precipitation of platinum up to 10,000 times more efficiently than any other common inorganic ligand, such as hydroxide, chloride, sulfate, or sulfide. Our results imply a far more important contribution of sulfur-bearing hydrothermal fluids to PGE transfer and accumulation in the Earth's crust than believed previously. This discovery challenges traditional models of PGE economic concentration from silicate and sulfide melts and provides new possibilities for resource prospecting in hydrothermal shallow crust settings. The exceptionally high capacity of the S3•- ion to bind platinum may also offer new routes for PGE selective extraction from ore and hydrothermal synthesis of noble metal nanomaterials.

Many-body effects at the origin of structural transitions in B2O3.

The structural properties of glassy diboron trioxide, g-B2O3, are investigated from ambient to high pressure conditions using two types of atomic force-field models that account for many-body effects. These models are parameterized by a dipole- and force-fitting procedure of reference datasets created via first-principles calculations on a series of configurations. The predictions of the models are tested against experimental data, where particular attention is paid to the structural transitions in g-B2O3 that involve changes to both the short- and medium-range order. The models outperform those previously devised, where improvement originates from the incorporation of two key physical ingredients, namely, (i) the polarizability of the oxide ion and (ii) the ability of an oxide ion to change both size and shape in response to its coordination environment. The results highlight the importance of many-body effects for accurately modeling this challenging system.

Sulfur radical species form gold deposits on Earth.

Current models of the formation and distribution of gold deposits on Earth are based on the long-standing paradigm that hydrogen sulfide and chloride are the ligands responsible for gold mobilization and precipitation by fluids across the lithosphere. Here we challenge this view by demonstrating, using in situ X-ray absorption spectroscopy and solubility measurements, coupled with molecular dynamics and thermodynamic simulations, that sulfur radical species, such as the trisulfur ion S3(-), form very stable and soluble complexes with Au(+) in aqueous solution at elevated temperatures (>250 °C) and pressures (>100 bar). These species enable extraction, transport, and focused precipitation of gold by sulfur-rich fluids 10-100 times more efficiently than sulfide and chloride only. As a result, S3(-) exerts an important control on the source, concentration, and distribution of gold in its major economic deposits from magmatic, hydrothermal, and metamorphic settings. The growth and decay of S3(-) during the fluid generation and evolution is one of the key factors that determine the fate of gold in the lithosphere.

Hidden polymorphs drive vitrification in B2O3.

Understanding the conditions that favour crystallization or vitrification of liquids has been a long-standing scientific problem. Another connected, and not yet well understood question is the relationship between the glassy and the various possible crystalline forms a system may adopt. In this context, B(2)O(3) represents a puzzling case. It is one of the best glass-forming systems despite an apparent lack of low-pressure polymorphism. Furthermore, the system vitrifies in a glassy form abnormally different from the only known crystalline phase at ambient pressure. Last but not least, it never crystallizes from the melt unless pressure is applied, an intriguing behaviour known as the crystallization anomaly. Here, by means of ab initio calculations, we discover the existence of previously unknown B(2)O(3) crystalline polymorphs with structural properties similar to the glass and formation energies comparable to the known ambient crystal. The energy degeneracy of the crystals, which is high at ambient pressure and suppressed under pressure, provides a framework to understand the system's ability to vitrify and the origin of the crystallization anomaly. This work reconciles the behaviour of B(2)O(3) with that from other glassy systems and reaffirms the role played by polymorphism in a system's ability to vitrify. Some of the predicted crystals are cage-like materials entirely made of three-fold rings, opening new perspectives for the synthesis of boron-based nanoporous materials.

Van der Waals effects in ab initio water at ambient and supercritical conditions.

Density functional theory (DFT) within the generalized gradient approximation (GGA) is known to poorly reproduce the experimental properties of liquid water. The poor description of the dispersion forces in the exchange correlation functionals is one of the possible causes. Recent studies have demonstrated an improvement in the simulated properties when they are taken into account. We present here a study of the effects on liquid water of the recently proposed semi-empirical correction of Grimme et al. [J. Chem. Phys. 132, 154104 (2010)]. The difference between standard and corrected DFT-GGA simulations is rationalized with a detailed analysis upon modifying an accurate parameterised potential. This allows an estimate of the typical range of dispersion forces in water. We also show that the structure and diffusivity of ambient-like liquid water are sensitive to the fifth neighbor position, thus highlighting the key role played by this neighbor. Our study is extended to water at supercritical conditions, where experimental and theoretical results are much more scarce. We show that the semi-empirical correction by Grimme et al. improves significantly, although somewhat counter-intuitively, both the structural and the dynamical description of supercritical water.

van der Waals Contribution to the Relative Stability of Aqueous Zn(2+) Coordination States.

Many properties of aqueous cations depend on their coordination state. However, the lack of long-range order and the dynamic character of aqueous solutions make it difficult to obtain information beyond average coordination parameters. A thorough understanding of the molecular-scale environment of aqueous cations usually requires a combination of experimental and theoretical approaches. In the case of Zn2+, significant discrepancies occur among theoretical investigations based on first-principles molecular dynamics (FPMD) or free-energy calculations, although experimental data consistently point to a dominant hexaaquo-zinc complex (Zn[H2O]6)2+ in pure water. In the present study, the aqueous speciation of zinc is theoretically investigated by combining FPMD simulations and free-energy calculations based on metadynamics and umbrella-sampling strategies. The simulations are carried out within the density functional theory (DFT) framework using for the exchange-correlation functional either a standard generalized gradient approximation (GGA) or a nonlocal functional (vdw-DF2) which includes van der Waals interactions. The theoretical environment of Zn is confronted to experiment by comparing calculated and measured X-ray absorption spectra. It is shown that the inclusion of van der Waals interactions is crucial for the correct modeling of zinc aqueous speciation, whereas GGA incorrectly favors tetraaquo- (Zn[H2O]4)2+ and pentaaquo-zinc (Zn[H2O]5)2+ complexes, results obtained with the vdW-DF2 functional show that the hexaaquo-zinc complex is more stable than the tetraaquo and pentaaquo-zinc complexes by 13 and by 4 kJ mol-1, respectively. These results highlight the critical importance of even subtle interactions for the correct balance of different coordination states in aqueous solutions. However, for a given coordination state, GGA leads to a reasonable description of the geometry of the aqueous complex.

Boroxol Rings in Liquid and Vitreous B2O3 from First Principles.

We investigate the structural and vibrational properties of glassy B2O3 using first-principles molecular dynamics simulations. In particular, we determine the boroxol rings fraction f for which there is still no consensus in the literature. Two numerical models containing either a low or a high level of boroxol rings are tested against a gamut of experimental probes (static structure factor, Raman, 11B and 17O NMR data). We show that only the boroxol-rich model (f=75%) can reproduce the full set of observables. Total-energy calculations show that at the glass density, boroxol-rich structures are favored by about 6 kcal/(mol boroxol). Finally, the liquid state is explored in the 2,000-4,000 K range and a reduction of f to 10%-20% is obtained.