Ab initio prediction of equilibrium boron isotope fractionation between minerals and aqueous fluids at high P and T

Over the last decade experimental studies have shown a large B isotope fractionation between materials carrying boron incorporated in trigonally and tetrahedrally coordinated sites, but the mechanisms responsible for producing the observed isotopic signatures are poorly known. In order to understand the boron isotope fractionation processes and to obtain a better interpretation of the experimental data and isotopic signatures observed in natural samples, we use first principles calculations based on density functional theory in conjunction with ab initio molecular dynamics and a new pseudofrequency analysis method to investigate the B isotope fractionation between B-bearing minerals (such as tourmaline and micas) and aqueous fluids containing H_3BO_3 and H_4BO_4- species. We confirm the experimental finding that the isotope fractionation is mainly driven by the coordination of the fractionating boron atoms and have found in addition that the strength of the produced isotopic signature is strongly correlated with the B-O bond length. We also demonstrate the ability of our computational scheme to predict the isotopic signatures of fluids at extreme pressures by showing the consistency of computed pressure-dependent beta factors with the measured pressure shifts of the B-O vibrational frequencies of H_3BO_3 and H_4BO_4- in aqueous fluid. The comparison of the predicted with measured fractionation factors between boromuscovite and neutral fluid confirms the existence of the admixture of tetrahedral boron species in neutral fluid at high P and T found experimentally, which also explains the inconsistency between the various measurements on the tourmaline-mica system reported in the literature. Our investigation shows that the calculated equilibrium isotope fractionation factors have an accuracy comparable to the experiments.Comment: 19 pages, 11 figures, Accepted for publication in Geochimica et Cosmochimica Act

Configurational constraints on glass formation in the liquid calcium aluminate system

International audienc

Structure of levitated Si-Ge melts studied by high-energy x-ray diffraction in combination with reverse Monte Carlo simulations

The short-range order in liquid Si, Ge and binary Six-Ge1-x alloys (x = 0.25, 0.50, 0.75) was studied by x-ray diffraction and reverse Monte Carlo simulations. Experiments were performed in the normal and supercooled liquid states by using the containerless technique of aerodynamic levitation with CO2 laser heating, enabling deeper supercooling of liquid Si and Si-Ge alloys than previously reported. The local atomic structure of liquid Si and Ge resembles the beta-tin structure. The first coordination numbers of about 6 for all compositions are found to be independent of temperature indicating the supercooled liquids studied retain this high-density liquid (HDL) structure. However, there is evidence of developing local tetrahedral ordering, as manifested by a shoulder on the right side of the first peak in S(Q) which becomes more prominent with increasing supercooling. This result is potentially indicative of a continuous transition from the stable HDL beta-tin (high pressure) phase, towards a metastable low-density liquid phase, reminiscent of the diamond (ambient pressure) structure

Structure of liquid tricalcium aluminate

International audienceThe atomic-scale structure of aerodynamically levitated and laser-heated liquid tricalcium aluminate (Ca 3 Al 2 O 6) was measured at 2073(30) K by using the method of neutron diffraction with Ca isotope substitution (NDIS). The results enable the detailed resolution of the local coordination environment around calcium and aluminum atoms, including the direct determination of the liquid partial structure factor, S CaCa (Q), and partial pair distribution function, g CaCa (r). Molecular dynamics (MD) simulation and reverse Monte Carlo (RMC) refinement methods were employed to obtain a detailed atomistic model of the liquid structure. The composition Ca 3 Al 2 O 6 lies at the CaO-rich limit of the CaO:Al 2 O 3 glass-forming system. Our results show that, although significantly depolymerized, liquid Ca 3 Al 2 O 6 is largely composed of AlO 4 tetrahedra forming an infinite network with a slightly higher fraction of bridging oxygen atoms than expected for the composition. Calcium-centered polyhedra exhibit a wide distribution of four-to sevenfold coordinated sites, with higher coordinated calcium preferentially bonding to bridging oxygens. Analysis of the MD configuration reveals the presence of ∼10 % unconnected AlO 4 monomers and Al 2 O 7 dimers in the liquid. As the CaO concentration increases, the number of these isolated units increases, such that the upper value for the glass-forming composition of CaO:Al 2 O 3 liquids could be described in terms of a percolation threshold at which the glass can no longer support the formation of an infinitely connected AlO 4 network

From Molten Calcium Aluminates through Phase Transitions to Cement Phases

Crystalline calcium aluminates are a critical setting agent in cement. To date, few have explored the microscopic and dynamic mechanism of the transitions from molten aluminate liquids, through the supercooled state to glassy and crystalline phases, during cement clinker production. Herein, the first in situ measurements of viscosity and density are reported across all the principal molten phases, relevant to their eventual crystalline structures. Bulk atomistic computer simulations confirm that thermophysical properties scale with the evolution of network substructures interpenetrating melts on the nanoscale. It is demonstrated that the glass transition temperature (T-g) follows the eutectic profile of the liquidus temperature (T-m), coinciding with the melting zone in cement production. The viscosity has been uniquely charted over 14 decades for each calcium-aluminate phase, projecting and justifying the different temperature zones used in cement manufacture. The fragile-strong phase transitions are revealed across all supercooled phases coinciding with heterogeneous nucleation close to 1.2T(g), where sintering and quenching occur in industrial-scale cement processing

Prediction of equilibrium Li isotope fractionation between minerals and aqueous solutions at high P and T: an efficient ab initio approach

The mass-dependent equilibrium stable isotope fractionation between different materials is an important geochemical process. Here we present an efficient method to compute the isotope fractionation between complex minerals and fluids at high pressure, P, and temperature, T, representative for the Earth's crust and mantle. The method is tested by computation of the equilibrium fractionation of lithium isotopes between aqueous fluids and various Li bearing minerals such as staurolite, spodumene and mica. We are able to correctly predict the direction of the isotope fractionation as observed in the experiments. On the quantitative level the computed fractionation factors agree within 1.0 permil with the experimental values indicating predictive power of ab initio methods. We show that with ab initio methods we are able to investigate the underlying mechanisms driving the equilibrium isotope fractionation process, such as coordination of the fractionating elements, their bond strengths to the neighboring atoms, compression of fluids and thermal expansion of solids. This gives valuable insight into the processes governing the isotope fractionation mechanisms on the atomic scale. The method is applicable to any state and does not require different treatment of crystals and fluids.Comment: 14 pages, 10 figures, accepted for publication in Geochimica et Cosmochimica Act

Structural transformations on vitrification in the fragile glass-forming system CaAl₂O₄

International audienceThe structure of the fragile glass-forming material CaAl 2 O 4 was measured by applying the method of neutron diffraction with Ca isotope substitution to the laser-heated aerodynamically levitated liquid at 1973(30) K and to the glass at 300(1) K. The results, interpreted with the aid of molecular dynamics simulations, reveal key structural modifications on multiple length scales. Specifically, there is a reorganization on quenching that leads to an almost complete breakdown of the AlO 5 polyhedra and threefold coordinated oxygen atoms present in the liquid, and to their replacement by a predominantly corner-sharing network of AlO 4 tetrahedra in the glass. This process is accompanied by the formation of branched chains of edge and face-sharing Ca-centered polyhedra that give cationic ordering on an intermediate length scale, where the measured coordination number for O around Ca is 6.0(2) for the liquid and 6.4(2) for the glass. Calcium aluminates ðCaOÞ x ðAl 2 O 3 Þ 1Àx (0 x 1) have been extensively studied on account of their geological , technological, and scientific importance [1-20]. For example, they are a significant component of the Earth's mantle so that the liquid structure is of interest for understanding magma-related processes [21], they are an integral component of aluminous cement [22], the glasses have a favorable infrared transmission window that extends up to a wavelength $6 m [23] giving them optical applications [24,25], and the rare-earth-metal-doped materials exhibit persistent luminescence [26]. From a glass physics perspective, calcium aluminates are very fragile glass for-mers [1,4] and, in contrast to strong network glass formers such as SiO 2 , large structural alterations should accompany the rapid change in viscosity and other dynamical properties as the glass transition temperature T g is approached [27]. Experimental information on the extent of structural transformation is therefore essential to understanding the processes occurring around T g and the material properties to which they are linked. An experimental exploration of liquid aluminates is, however, challenging because of the high temperatures involved. The containerless method of aerodynamic levitation offers a way forward, and by minimizing heterogeneous nucleation, it extends the narrow glass-forming region centered at x ¼ 0:65 in the calcium aluminate system to include the equimolar composition CaAl 2 O 4 [16] which has a fragility index of m ¼ 116 [1,28]. At this composition , the O:Al ratio is 2:1 such that it is just feasible to form an ideal network of fully connected corner-sharing AlO 4 tetrahedra where the oxygen atoms are twofold coordinated, as in the crystalline phase which has a tridymite-like structure where the tetrahedra form a fully polymerized network of six-membered rings [29]. This has motivated a range of experimental and computer simulation studies on the liquid and glass structure [2-20]. It has, however, proved difficult to measure unambiguously the Al and Ca coordination environments. For example, in the liquid state 27 Al nuclear magnetic resonance (NMR) experiments observe the fast exchange limit such that individual Al coordination environments cannot be identified [2-5], and in diffraction experiments , the nearest-neighbor Ca-O and other pair correlations are strongly overlapped [16-19]. The powerful method of neutron diffraction with isotope substitution has been used to probe directly the coordination environment of Ca in ðCaOÞ 48 ðSiO 2 Þ 49 ðAl 2 O 3 Þ 3 glass [30,31], but the method is usually limited to large samples [32]. In this Letter we show, however, that the neutron diffraction with isotope substitution method can be used to measure the detailed atomic structure of a single aerodynamically levitated laser-heated drop of liquid CaAl 2 O 4 at 1973(30) K. The structure of the glass at 300(1) K is also investigated. The results, interpreted with the aid of molecular dynamics (MD) simulations, characterize the nature of the structural transformations that occur on vitrification on both the local and intermediate atomic length scales. The total structure factor measured by neutron diffraction is given by FðQÞ ¼ P P c c b b ½S ðQÞ À 1

Hydration in aqueous NaCl

Atomistic details about the hydration of ions in aqueous solutions are still debated due to the disordered and statistical nature of the hydration process. However, many processes from biology, physical chemistry to materials sciences rely on the complex interplay between solute and solvent. Oxygen K-edge X-ray excitation spectra provide a sensitive probe of the local atomic and electronic surrounding of the excited sites. We used ab initio molecular dynamics simulations together with extensive spectrum calculations to relate the features found in experimental oxygen K-edge spectra of a concentration series of aqueous NaCl with the induced structural changes upon solvation of the salt and distill the spectral fingerprints of the first hydration shells around the Na+- and Cl−-ions. By this combined experimental and theoretical approach, we find the strongest spectral changes to indeed result from the first hydration shells of both ions and relate the observed shift of spectral weight from the post- to the main-edge to the origin of the post-edge as a shape resonance. </p