Cooperative excitations in superionic PbF.

Links between dynamical Frenkel defects and collective diffusion of fluorides in -PbF are explored using Born-Oppenheimer molecular dynamics. The calculated self-diffusion coefficient and ionic conductivity are 3.2 × 10 cm s and 2.

Fast-ion conduction and local environments in BIMEVOX.

The energy landscape of the fast-ion conductor BiVO is studied using density functional theory. There are a large number of energy minima, dominated by low-lying thermally accessible configurations in which there are equal numbers of oxygen vacancies in each vanadium-oxygen layer, a range of vanadium coordinations and a large variation in Bi-O and V-O distances. By dividing local minima in the energy landscape into sets of configurations, we then examine diffusion in each different layer using molecular dynamics.

First principles calculations on order and disorder in LaCeO and NdCeO.

In this paper, we highlight the connection between the local structure and collective dynamics of the defective fluorites LaCeO and NdCeO. The local and average structure is explored by investigating a large number of different structural models and snapshots from Born-Oppenheimer Molecular dynamics calculations. Both compounds show a strong preference for local oxygen vacancy order similar to that found in the C-type structure.

C-type related order in the defective fluorites La2Ce2O7 and Nd2Ce2O7 studied by neutron scattering and ab initio MD simulations.

This work presents a structural investigation of La2-xNdxCe2O7 (x = 0.0, 0.5, 1.

Predicting complex mineral structures using genetic algorithms.

We show that symmetry-adapted genetic algorithms are capable of finding the ground state of a range of complex crystalline phases including layered- and incommensurate super-structures. This opens the way for the atomistic prediction of complex crystal structures of functional materials and mineral phases.

Neutron total scattering study of the delta and beta phases of Bi2O3.

The highly disordered structure of the delta phase of Bi2O3, which possesses the highest known oxide-ion conductivity, has been studied using neutron powder diffraction. A detailed analysis of data collected at 1033(3) K using Rietveld refinement indicates that the time-averaged structure of delta-Bi2O3 can be described using the accepted model of a disordered, anion-deficient fluorite structure in space group Fm3m. However, reverse Monte Carlo modelling of the total (Bragg plus diffuse) scattering demonstrates that the local anion environment around the Bi3+ resembles the distorted square pyramidal arrangement found within the stable alpha and metastable beta phases at ambient temperature, which is characteristic of the cation's 6s2 lone-pair configuration.

Diffusion within α-CuI studied using ab initio molecular dynamics simulations.

The structure and dynamics of superionic α-CuI are studied in detail by means of ab initio Born-Oppenheimer molecular dynamics simulations. The extreme cation disorder and a soft immobile face centred cubic sublattice are evident from the highly diffuse atomic density profiles. The Cu-Cu pair distribution function and distribution of Cu-I-Cu bond angles possess distinct peaks at 2.

Oxide-ion disorder within the high temperature delta phase of Bi2O3.

The delta phase of Bi(2)O(3), which adopts an anion-deficient fluorite structure, has the highest known oxide-ion conductivity. Using a combination of neutron powder diffraction and Born-Oppenheimer molecular dynamics, the preferred local anion environment around the Bi(3+) within delta-Bi(2)O(3) is shown to be highly irregular, resembling the asymmetric "lone-pair" coordination found within many (fully ordered) oxides of Bi(3+) under ambient conditions. The asymmetric electron density around the Bi(3+) plays a central role in promoting the extreme anion disorder within delta-Bi(2)O(3), with the ion diffusion facilitated by extensive relaxations of both the surrounding anions and a "soft" cation sublattice.

Ultrathin oxide films and heterojunctions: CaO layers on BaO and SrO.

We examine the form of the islands formed by CaO on BaO and SrO substrates using both periodic density functional theory and atomistic simulation techniques. (100) edges dominate the island morphology and we examine how the CaO adjusts to the substrate in small and medium sized islands and at much larger coverages. There is no direct overlay of CaO ion pairs over OBa or OSr pairs in the top substrate layer.

Topography of the potential energy hypersurface and criteria for fast-ion conduction in perovskite-related A2B2O5 oxides.

We discuss the importance of the topography of the potential energy hypersurface for the ionic conductivity of perovskite-related A(2)B(2)O(5) oxides. A correlation between the energetic preference of the cations for different coordination geometries and the ionic conductivity is proposed based on a first principles periodic density functional theory study of selected possible structures for Ba(2)In(2)O(5), Sr(2)Fe(2)O(5), Sr(2)Mn(2)O(5), and La(2)Ni(2)O(5). There are a large number of low-energy local minima on the potential energy hypersurfaces of the two first compounds due to an energetic preference for BO(4) tetrahedra.

What can a "quantum black-box" do for the inorganic thermochemist?

Enthalpies of formation of ABO3 (A = Ca, Sr, Ba; B = Ti, Zr, Hf) from the binary constituent oxides have been calculated by ab initio density functional theory. The resulting values compare well with the large number of experimental determinations reported in literature. The trends in the calculated enthalpies of formation correlate with the difference in acidity between the binary constituent oxides.

Oxygen-deficient perovskites: linking structure, energetics and ion transport.

The present review focuses on links between structure, energetics and ion transport in oxygen-deficient perovskite oxides, ABO(3-delta). The perfect long-range order, convenient for interpretations of the structure and properties of ordered materials, is evidently not present in disordered materials and highly defective perovskite oxides are spatially inhomogeneous on an intermediate length scale. Although this makes a fundamental description of these and other disordered materials very difficult, it is becoming increasingly clear that this complexity is often essential for the functional properties.

Genetic mapping of the distribution of minima on the potential energy surface of disordered systems.

We show that genetic algorithms and energy minimizations in combination provide a highly efficient tool for mapping low-energy minima on the erratic and complex potential-energy surfaces of grossly disordered materials. The distribution of energy minima mimics with sufficient accuracy the low-energy portion of the parent distribution of minima and allows accurate calculation of configurational Boltzmann averaged structural and thermodynamic properties in cases where a small fraction of the minima is thermally accessible. The distribution of energy minima obtained using genetic algorithms is biased, and consequently the properties converge slowly at high temperatures.

The Rotational g Tensor as a Benchmark for Density-Functional Theory Calculations of Molecular Magnetic Properties.

The rotational g factor for a large number of organic compounds has been investigated with density-functional theory. Rapid convergence toward the basis-set limit is ensured by the use of London atomic orbitals. A statistical analysis of the results has been carried out in comparison with accurate experimental data.

Size mismatch effects in oxide solid solutions using Monte Carlo and configurational averaging.

Local minima configurational averaging (CA) and Monte Carlo (MC) simulations are used to examine in detail the variation of thermodynamic and structural properties of binary oxide solid solutions with the volume mismatch between the end members. The maximum volume mismatch studied corresponds to that in the CaO MgO solid solution, a prototype example of a strongly non-ideal system with large miscibility gap. In addition, solid solutions of CaO-HypO using designed hypothetical atoms (Hyp) with atomic radii between those of Ca2+ and Mg2+ have been considered.