Structure of amorphous Ag/Ge/S alloys: experimentally constrained density functional study.

Density functional/molecular dynamics simulations have been performed to determine structural and other properties of amorphous Ag/Ge/S and Ge/S alloys. In the former, the calculations have been combined with experimental data (x-ray and neutron diffraction, extended x-ray absorption fine structure). Ag/Ge/As alloys have high ionic conductivity and are among the most promising candidates for future memristor technology. We find excellent agreement between the experimental results and large-scale (500 atoms) simulations in Ag/Ge/S, and we compare and contrast the structures of Ge/S and Ag/Ge/S. The calculated electronic structures, vibrational densities of states, ionic mobilities, and cavity distributions of the amorphous materials are discussed and compared with data on crystalline phases where available. The high mobility of Ag in solid state electrolyte applications is related to the presence of cavities and can occur via jumps to a neighbouring vacant site.

Liquid structure and temperature invariance of sound velocity in supercooled Bi melt.

Structural rearrangement of liquid Bi in the vicinity of the melting point has been proposed due to the unique temperature invariant sound velocity observed above the melting temperature, the low symmetry of Bi in the solid phase and the necessity of overheating to achieve supercooling. The existence of this structural rearrangement is examined by measurements on supercooled Bi. The sound velocity of liquid Bi was measured into the supercooled region to high accuracy and it was found to be invariant over a temperature range of ∼60°, from 35° above the melting point to ∼25° into the supercooled region. The structural origin of this phenomenon was explored by neutron diffraction structural measurements in the supercooled temperature range. These measurements indicate a continuous modification of the short range order in the melt. The structure of the liquid is analyzed within a quasi-crystalline model and is found to evolve continuously, similar to other known liquid pnictide systems. The results are discussed in the context of two competing hypotheses proposed to explain properties of liquid Bi near the melting: (i) liquid bismuth undergoes a structural rearrangement slightly above melting and (ii) liquid Bi exhibits a broad maximum in the sound velocity located incidentally at the melting temperature.

Acidic properties of aqueous phosphoric acid solutions: a microscopic view.

We report on new neutron and x-ray diffraction data on D2O:D3PO4 solutions at two concentrations, 1:1 and 3:1. The experimental datasets were modelled simultaneously by the reverse Monte Carlo (RMC) method. From the resulting models, partial radial distribution functions (prdf) and coordination numbers were obtained. The acidity was found to decrease with increasing D3PO4 concentration. The ratio of dissociated acidic protons was estimated by dedicated simulation runs using average coordination number constraints. It was found that in the saturated solution the ratio of dissociated protons cannot exceed 20%.

Silver environment and covalent network rearrangement in GeS3-Ag glasses.

The structure of Ag-doped GeS3 glasses (0, 15, 20, 25 at.% Ag) was investigated by diffraction techniques and extended x-ray absorption fine structure measurements. Structural models were obtained by fitting the experimental datasets simultaneously by the reverse Monte Carlo simulation technique. It is observed that Ge has mostly S neighbours in GeS3, but Ge-Ge bonds appear already at 15% Ag content. Sulfur has ~2 S/Ge neighbours over the whole concentration range, while the S-Ag coordination number increases with increasing Ag content. Ag-Ag pairs can already be found at 15% Ag. The Ag-S mean coordination number changes from 2.17 ± 0.2 to 2.86 ± 0.2 between 15% and 25% Ag content. Unlike the As-S network in AsS2-25Ag glass, the Ge-S network is not fragmented upon Ag-doping of GeS3 glass.

The non-Gaussian dynamics of glycerol.

We have combined incoherent quasielastic neutron scattering experiments and atomistic molecular simulations to investigate the microscopic dynamics of glycerol moving away from the hydrodynamic limit. We relate changes in the momentum transfer (Q) dependence of the relaxation time to distinct changes of the single-particle dynamics. Going from small to large values of Q, a first crossover at about 0.5 Å(-1) is related to the coupling of the translational diffusion dynamics to the non-Debye structural relaxation, while the second crossover at a Q-value near the main diffraction peak is associated with the Gaussian to non-Gaussian crossover of the short-time molecular dynamics, related to the decaging processes. We offer an unprecedented extension of previous studies on polymeric systems towards the case of the typical low-molecular-weight glass-forming system glycerol.

Influence of rare-earth ions on SiO2-Na2O-RE2O3 glass structure.

Praseodymium and europium sodium silicate glasses of nominal composition (SiO(2))(0.70 - x)(Na(2)O)(0.30)(RE(2)O(3))(x), where RE is the rare earth and 0 ≤ x ≤ 0.10, were studied by neutron and high-energy x-ray scattering and classical molecular dynamics simulations. The observation of a significant x-ray intensity in doped as compared to un-doped glasses is indicative of RE-RE correlations at a distance of ∼ 3.7-3.9 Å, much shorter than would be expected for a homogeneous distribution, suggesting that clustering of the rare-earth cations occurs in both these glass systems at low concentrations. Above x = 0.075 (nominal), minimal changes in this region indicate that the RE atoms are incorporated much more randomly into the glass structure. The molecular dynamics simulations suggest that the rare-earth ions enter the sodium-rich regions in the sodium silicate glasses and act as modifiers. A cluster analysis performed on the model systems indicates that the tendency for clustering is higher in praseodymium-containing glasses than in the europium glasses.

Structure of GeSe4-In and GeSe5-In glasses.

(Ge(0.2)Se(0.8))(100-x)In(x) and (Ge(0.17)Se(0.83))(100-x)In(x) (x = 0, 5, 10, 15 at.%) chalcogenide glasses have been studied with high-energy x-ray diffraction, neutron diffraction and extended x-ray absorption spectroscopy at Ge, Se and In K-edges. The experimental data were modelled simultaneously with the reverse Monte Carlo simulation method. GeSe(4/2) tetrahedra are shown to be the main structural units in the binary and ternary glasses investigated. Indium bonds to the excess Se atoms in the ternary Ge-Se-In glasses. While the majority of In atoms have three Se neighbours, some In atoms may be tetrahedrally coordinated by Se.

On the atomic structure of Zr60Cu20Fe20 metallic glass.

The structure of Zr(60)Cu(20)Fe(20) metallic glass has been studied with high-energy x-ray diffraction, neutron diffraction and extended x-ray absorption spectroscopy and modelled with the reverse Monte Carlo simulation technique. It is found that Cu and Fe atoms prefer Zr as a nearest neighbour. The mean interatomic distance between Cu/Fe and Zr atoms in the glass is remarkably shorter than the sum of the respective atomic radii. The coordination numbers for Cu/Fe-Cu/Fe pairs are very close to each other, suggesting a regular distribution of Cu and Fe atoms in the Zr(60)Cu(20)Fe(20) metallic glass.

Atomic structure of As(2)S(3)-Ag chalcogenide glasses.

(As(0.4)S(0.6))(100-x)Ag(x) glasses (x = 0, 4, 8, 12 at.%) have been studied with high-energy x-ray diffraction, neutron diffraction and extended x-ray absorption spectroscopy at As and Ag K-edges. The experimental data were modelled simultaneously with the reverse Monte Carlo simulation method. Analysis of the partial pair correlation functions and coordination numbers extracted from the model atomic configurations revealed that silver preferentially bonds to sulfur in the As(2)S(3)-Ag ternary glasses, which results in the formation of homoatomic As-As bonds. Upon the addition of Ag, a small proportion of Ag-As bonds (N(AgAs)≈0.3) are formed in all three ternary compositions, while the direct Ag-Ag bonds (N(AgAg)≈ 0.4) appear only in the glass with the highest Ag content (12 at.%). Similar to the g- As(2)S(3) binary, the mean coordination number of arsenic is close to three, and that of sulfur is close to two, in the As(2)S(3)-Ag ternary glasses. The first sharp diffraction peak on the total structure factors of As(2)S(3) binary and (As(0.4)S(0.6))(100-x)Ag(x) ternary glasses is related to the As-As and As-S correlations.

Structure of As(x)Te(100-x) (20

A systematic and detailed investigation of the structure of As(x)Te(100-x) glasses (20

'Wrong bonds' in sputtered amorphous Ge(2)Sb(2)Te(5).

The structure of sputtered amorphous Ge(2)Sb(2)Te(5) was investigated by high energy x-ray diffraction, neutron diffraction and Ge-, Sb- and Te K-edge EXAFS measurements. The five datasets were modelled simultaneously in the framework of the reverse Monte Carlo simulation technique. It was found that apart from Te-Sb and Te-Ge bonds existing in the crystalline phases, Ge-Ge and Sb-Ge bonding is also significant in sputtered amorphous Ge(2)Sb(2)Te(5). According to our results, all components obey the '8-N' rule.