Iron coordination in liquid FeAl2O4.

The structure of aerodynamically levitated liquid [Formula: see text] was measured by neutron diffraction with isotope substitution (NDIS). Classical and ab initio molecular dynamics simulations were performed and their results were found to be in close agreement with each other and the NDIS data. The results reveal that molten [Formula: see text] may be considered as an ionic liquid without any preference for particular short-range structural motifs. This article is part of the theme issue 'Exploring the length scales, timescales and chemistry of challenging materials (Part 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.

Ion association in hydrothermal aqueous NaCl solutions: implications for the microscopic structure of supercritical water.

Knowledge of the microscopic structure of fluids and changes thereof with pressure and temperature is important for the understanding of chemistry and geochemical processes. In this work we investigate the influence of sodium chloride on the hydrogen-bond network in aqueous solution up to supercritical conditions. A combination of in situ X-ray Raman scattering and ab initio molecular dynamics simulations is used to probe the oxygen K-edge of the alkali halide aqueous solution in order to obtain unique information about the oxygen's local coordination around the ions, e.g. solvation-shell structure and the influence of ion pairing. The measured spectra exhibit systematic temperature dependent changes, which are entirely reproduced by calculations on the basis of structural snapshots obtained via ab initio molecular dynamics simulations. Analysis of the simulated trajectories allowed us to extract detailed structural information. This combined analysis reveals a net destabilizing effect of the dissolved ions which is reduced with rising temperature. The observed increased formation of contact ion pairs and occurrence of larger polyatomic clusters at higher temperatures can be identified as a driving force behind the increasing structural similarity between the salt solution and pure water at elevated temperatures and pressures with drawback on the role of hydrogen bonding in the hot fluid. We discuss our findings in view of recent results on hot NaOH and HCl aqueous fluids and emphasize the importance of ion pairing in the interpretation of the microscopic structure of water.

Beyond sixfold coordinated Si in SiO2 glass at ultrahigh pressures.

We investigated the structure of SiO2 glass up to 172 GPa using high-energy X-ray diffraction. The combination of a multichannel collimator with diamond anvil cells enabled the measurement of structural changes in silica glass with total X-ray diffraction to previously unachievable pressures. We show that SiO2 first undergoes a change in Si-O coordination number from fourfold to sixfold between 15 and 50 GPa, in agreement with previous investigations. Above 50 GPa, the estimated coordination number continuously increases from 6 to 6.8 at 172 GPa. Si-O bond length shows first an increase due to the fourfold to sixfold coordination change and then a smaller linear decrease up to 172 GPa. We reconcile the changes in relation to the oxygen-packing fraction, showing that oxygen packing decreases at ultrahigh pressures to accommodate the higher than sixfold Si-O coordination. These results give experimental insight into the structural changes of silicate glasses as analogue materials for silicate melts at ultrahigh pressures.

Aqueous sodium hydroxide (NaOH) solutions at high pressure and temperature: insights from in situ Raman spectroscopy and ab initio molecular dynamics simulations.

Hydrothermal diamond anvil cell experiments in combination with Raman spectroscopy and first principles molecular dynamics simulations were performed to investigate the structure and dynamics of aqueous NaOH solutions for temperatures up to 700 °C, pressures up to 850 MPa and two different solute concentrations. The significant changes observed in the O-H stretching region of the Raman spectra between ambient and supercritical conditions are explained by both dynamic effects and structural differences. Especially important are a Grotthuss-like proton transport process and the decreasing network connectivity of the water molecules with increasing temperature. The observed transfer of Raman intensity towards lower wavenumbers by the proton transfer affects a wide range of frequencies and must be considered in the interpretation of Raman spectra of highly basic solutions. We suggest a deconvolution of the spectra using a model with four Gaussian functions, which are assigned to the molecular H2O and OH- vibrations, and one asymmetric exponentially modified Gaussian (EMG) function, which is assigned to [HO(H2O)n]- vibrations.

Microscopic structure of water at elevated pressures and temperatures.

We report on the microscopic structure of water at sub- and supercritical conditions studied using X-ray Raman spectroscopy, ab initio molecular dynamics simulations, and density functional theory. Systematic changes in the X-ray Raman spectra with increasing pressure and temperature are observed. Throughout the studied thermodynamic range, the experimental spectra can be interpreted with a structural model obtained from the molecular dynamics simulations. A spatial statistical analysis using Ripley's K-function shows that this model is homogeneous on the nanometer length scale. According to the simulations, distortions of the hydrogen-bond network increase dramatically when temperature and pressure increase to the supercritical regime. In particular, the average number of hydrogen bonds per molecule decreases to ≈ 0.6 at 600 °C and p = 134 MPa.

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

The 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.

Vibrational mode frequencies of silica species in SiO2-H2O liquids and glasses from ab initio molecular dynamics.

Vibrational spectroscopy techniques are commonly used to probe the atomic-scale structure of silica species in aqueous solution and hydrous silica glasses. However, unequivocal assignment of individual spectroscopic features to specific vibrational modes is challenging. In this contribution, we establish a connection between experimentally observed vibrational bands and ab initio molecular dynamics (MD) of silica species in solution and in hydrous silica glass. Using the mode-projection approach, we decompose the vibrations of silica species into subspectra resulting from several fundamental structural subunits: The SiO(4) tetrahedron of symmetry T(d), the bridging oxygen (BO) Si-O-Si of symmetry C(2v), the geminal oxygen O-Si-O of symmetry C(2v), the individual Si-OH stretching, and the specific ethane-like symmetric stretching contribution of the H(6)Si(2)O(7) dimer. This allows us to study relevant vibrations of these subunits in any degree of polymerization, from the Q(0) monomer up to the fully polymerized Q(4) tetrahedra. Demonstrating the potential of this approach for supplementing the interpretation of experimental spectra, we compare the calculated frequencies to those extracted from experimental Raman spectra of hydrous silica glasses and silica species in aqueous solution. We discuss observed features such as the double-peaked contribution of the Q(2) tetrahedral symmetric stretch, the individual Si-OH stretching vibrations, the origin of the experimentally observed band at 970 cm(-1) and the ethane-like vibrational contribution of the H(6)Si(2)O(7) dimer at 870 cm(-1).

Vibrational mode frequencies of H4SiO4, D4SiO4, H6Si2O7, and H6Si3O9 in aqueous environment, obtained from ab initio molecular dynamics.

We report the vibrational properties of H(4)SiO(4), D(4)SiO(4), H(6)Si(2)O(7), and H(6)Si(3)O(9) in aqueous solution at 300 K and 1000 K, obtained from the combination of ab initio molecular dynamics (MD) and a mode-decomposition approach. This combination yields vibrational subspectra for selected vibrational modes at finite temperatures. We also performed normal-mode analysis (NMA) on numerous configurations from the same MD run to sample the effect of the variable molecular environment. We found good agreement between both approaches. The strongest effect of temperature is on the SiOH bending mode δSiOH, which is at about 1145 cm(-1) in solution at 300 K, opposed to about 930 cm(-1) in solution at 1000 K. The frequency of the δSiOH vibration also depends on environment, shifting from 1145 cm(-1) in solution to about 845 cm(-1) in the gas-phase. We found both in the mode-decomposition approach and in multiple-configuration NMA that the H(6)Si(2)O(7) dimer shows a vibrational mode at about 790 cm(-1), which we consider to be responsible for a hitherto unexplained shoulder of the monomer Raman band at 770 cm(-1) in dilute silica solutions. Our results demonstrate the importance of temperature and solvation environment in calculations that aim to support the interpretation of experimental Raman spectra of dissolved silica.

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-xalloys (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 CO2laser heating, enabling deeper supercooling of liquid Si and Si-Ge alloys than previously reported. The local atomic structure of liquid Si and Ge resembles theß-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 inS(Q) which becomes more prominent with increasing supercooling. This result is potentially indicative of a continuous transition from the stable HDLß-tin (high pressure) phase, towards a metastable low-density liquid phase, reminiscent of the diamond (ambient pressure) structure.

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.

Cation Hydration in Supercritical NaOH and HCl Aqueous Solutions.

We present a study of the local atomic environment of the oxygen atoms in the aqueous solutions of NaOH and HCl under simultaneous high-temperature and high-pressure conditions. Experimental nonresonant X-ray Raman scattering core-level spectra at the oxygen K-edge show systematic changes as a function of temperature and pressure. These systematic changes are distinct for the two different solutes and are described well by calculations within the Bethe-Salpeter formalism for snapshots from ab initio molecular dynamics simulations. The agreement between experimental and simulation results allows us to use the computations for a detailed fingerprinting analysis in an effort to elucidate the local atomic structure and hydrogen-bonding topology in these relevant solutions. We observe that both electrolytes, especially NaOH, enhance hydrogen bonding and tetrahedrality in the water structure at supercritical conditions, in particular in the vicinity of the hydration shells. This effect is accompanied with the association of the HCl and NaOH molecules at elevated temperatures.

From atomic structure to excess entropy: a neutron diffraction and density functional theory study of CaO-Al2O3-SiO2 melts.

Calcium aluminosilicate CaO-Al2O3-SiO2 (CAS) melts with compositions (CaO-SiO2)(x)(Al2O3)(1-x) for x < 0.5 and (Al2O3)(x)(SiO2)(1-x) for x ≥ 0.5 are studied using neutron diffraction with aerodynamic levitation and density functional theory molecular dynamics modelling. Simulated structure factors are found to be in good agreement with experimental structure factors. Local atomic structures from simulations reveal the role of calcium cations as a network modifier, and aluminium cations as a non-tetrahedral network former. Distributions of tetrahedral order show that an increasing concentration of the network former Al increases entropy, while an increasing concentration of the network modifier Ca decreases entropy. This trend is opposite to the conventional understanding that increasing amounts of network former should increase order in the network liquid, and so decrease entropy. The two-body correlation entropy S2 is found to not correlate with the excess entropy values obtained from thermochemical databases, while entropies including higher-order correlations such as tetrahedral order, O-M-O or M-O-M bond angles and Q(N) environments show a clear linear correlation between computed entropy and database excess entropy. The possible relationship between atomic structures and excess entropy is discussed.

Development of chemical and topological structure in aluminosilicate liquids and glasses at high pressure.

The high pressure structure of liquid and glassy anorthite (CaAl(2)Si(2)O(8)) and calcium aluminate (CaAl(2)O(4)) glass was measured by using in situ synchrotron x-ray diffraction in a diamond anvil cell up to 32.4(2) GPa. The results, combined with ab initio molecular dynamics and classical molecular dynamics simulations using a polarizable ion model, reveal a continuous increase in Al coordination by oxygen, with 5-fold coordinated Al dominating at 15 GPa and a preponderance of 6-fold coordinated Al at higher pressures. The development of a peak in the measured total structure factors at 3.1 Å(-1) is interpreted as a signature of changes in topological order. During compression, cation-centred polyhedra develop edge- and face- sharing networks. Above 10 GPa, following the pressure-induced breakdown of the network structure, the anions adopt a structure similar to a random close packing of hard spheres.

The structure of liquid calcium aluminates as investigated using neutron and high energy x-ray diffraction in combination with molecular dynamics simulation methods.

The structure of laser heated aerodynamically levitated (CaO)(x)(Al2O3)(1-x) high temperature liquids, with x = 0.33, 0.5, 0.75, was measured by using neutron and high energy x-ray diffraction. The partial structure factors for the liquids at 2500 K were also determined using molecular dynamics computer simulations. The simulation results are in excellent agreement with the diffraction measurements. The results show a predominant tetrahedral Al coordination with approximately 20% of fivefold coordinated Al at x = 0.33 which reduces with increasing CaO concentration. The Ca atoms occupy a broad range of coordination environments but with a predominance of sixfold distorted octahedra. The simulations confirm the presence of 13, 7 and 0.6% OAl3 triclusters connecting AlO4 tetrahedra in the structure of CA2 (x = 0.33), CA (x = 0.5) and C3A (x = 0.75) liquids, respectively.

Integral modeling approach to study the phase behavior of complex solids: application to phase transitions in MgSiO3 pyroxenes.

A combination of electronic structure calculations, classical molecular dynamics simulations and metadynamics is proposed to study the phase behavior of complex crystals. While the former provide accurate energetics for thermodynamic properties, molecular dynamics and metadynamics simulations may reveal new metastable phases and provide insight into mechanisms and kinetics of the respective structural transformations. Here, different simulation methods are used to investigate the polymorphism of MgSiO(3) pyroxenes (enstatites) up to high pressures and temperatures. A number of displacive phase transitions are observed within the three basic structure types clino-, ortho- and protoenstatite using classical molecular dynamics simulations. Transitions between these types require a change of stacking order, which is modeled using a combination of molecular dynamics and metadynamics.

Speciation in aqueous MgSO(4) fluids at high pressures and high temperatures from ab initio molecular dynamics and Raman spectroscopy.

Ab initio molecular dynamics simulations and in situ Raman spectroscopy are used to study the speciation in two molal aqueous MgSO4 solutions at high pressures, P, and temperatures, T. While at ambient conditions the fluid is dominated by dissociated SO42−(aq) ions and solvent-separated ion pairs, ion association strongly increases with increasing temperature and pressure along a 1.33 g/cm3 isochore. At T = 450 °C and P = 1.4GPa, the ν1(SO42−) Raman band is well described by three Gaussian + Lorentzian components of about equal intensity with peaks at about 980, 995, and 1005 cm−1. Analysis of the simulations, however, indicates the coexistence of more than three species, including dissociated SO42−(aq) ions, and contact and triple ion pairs as well as larger complexes. In addition, the sulfate groups may be bonded to Mg as monodentate or bidentate ligands. The frequencies of the associated species seem to depend mainly on the type and number of Mg−SO4 bonds. We interpret the two rather broad high-frequency Raman components as a single "Mg−SO4 contact" component with variable frequency distribution. As a consequence, the ν1(SO42−) Raman band provides only information on the molecular environment of the sulfate group; i.e., individual species cannot be resolved. At fluid densities less than about 1.2 g/cm3 and temperatures above 400 °C, the formation of HSO4−(aq)-containing species is observed in both simulations and experiments, which may be accompanied by a change in pH and electrical conductivity.

Condensed phase ionic polarizabilities from plane wave density functional theory calculations.

A method is presented to allow the calculation of the dipole polarizabilities of ions and molecules in a condensed-phase coordination environment. These values will be useful for understanding the optical properties of materials and for developing simulation potentials which incorporate polarization effects. The reported values are derived from plane wave density functional theory calculations, though the method itself will apply to first-principles calculations on periodic systems more generally. After reporting results of test calculations on atoms to validate the procedure, values for the polarizabilities of the oxide ion and various cations in a range of materials are reported and compared with experimental information as well as previous theoretical results.

Atomic dynamics in liquids with competing interactions.

The influence of the type of atomic interaction on the atomic dynamics is studied for liquid Na(x)Sn(1-x) (x = 0.9, 0.77, 0.57, 0.5, 0.33) alloys by cold neutron inelastic scattering. The dispersions obtained from the longitudinal current correlation function J(l)(Q,omega) show clear evidence for the dependence of the dynamics on the type of interaction (metallic, ionic, partly covalent) tuned by changing the composition of the alloy. For the first time, a second dispersion branch is observed in the total J(l)(Q,omega) around Q(p), the position of the principal peak of S(Q), for the Sn-rich compositions. The dynamic properties are discussed and compared to results of recent ab initio molecular dynamics simulations.

Multipoles and interaction potentials in ionic materials from planewave-DFT calculations.

Oxide potentials which transfer well between different materials have to account explicitly for many-body contributions to the interaction potentials between the ions. These include dipole and quadrupole polarization effects and the compression and deformation of an oxide ion by its immediate coordination environment. Such complex potentials necessarily involve many parameters. We examine how the results of ab initio electronic structure calculations, based upon planewave DFT methods, on general configurations of ions derived from simulations at finite temperature, may be used to parameterize an "aspherical ion method" (AIM) potential (A. J. Rowley, P. Jemmer, M. Wilson and P. A. Madden, J Chem. Phys., 1998, 108, 10209). Dipoles and quadrupoles on the individual ions are obtained via a transformation of the Kohn Sham orbitals to localized orbitals on each ion, which enables a distorted charge density for each ion to be obtained. The dipoles and quadrupoles appearing in polarization parts of the AIM potential are fit to those obtained from the ab initio ionic charge densities obtained in this way. The remaining parts of the potential, describing short-range repulsive interactions between ions with compressed and deformed charge densities, are fit to the ab initio forces and the stress tensor. By using a sufficiently large and varied set of configurations on which to carry out this optimization, an excellent transferable potential is obtained.