Thomas Hammerschmidt

Possible routes for synthesis of new boron-rich Fe–B and Fe1−xCrxB4 compounds

We use ab initio calculations to examine thermodynamic factors that could promote the formation of recently proposed unique oP10-FeB4 and oP12-FeB2 compounds. We demonstrate that these compact boron-rich phases are stabilized further under pressure. We also show that chromium tetraboride is more stable in the new oP10 rather than the reported oI10 structure which opens up the possibility of realizing an oP10-(FexCr1−x)B4 pseudobinary material. In addition to exhibiting remarkable electronic features, oP10-FeB4 and oP12-FeB2 are expected to be harder than the known Fe–B compounds commonly used for hard coating applications.

Microsegregation and precipitates of an as-cast Co-based superalloy—microstructural characterization and phase stability modelling

The demand for increased efficiency of industrial gas turbines and aero engines drives the search for the next generation of materials. Promising candidates for such new materials are Co-based superalloys. We characterize the microsegregation and solidification of a multi-component Co-based superalloy and compare it to a ternary Co–Al–W compound and to two exemplary Ni-based superalloys by combining the experimental characterization of the as-cast microstructures with complementary modelling of phase stability. On the experimental side, we characterize the microstructure and precipitates by electron microscopy and energy-dispersive X-ray spectroscopy and determine the element distributions and microsegregation coefficients by electron probe microanalysis (EPMA). On the modelling side, we carry out solidification simulations and a structure map analysis in order to relate the local chemical composition with phase stability. We find that the microsegregation coefficients for the individual elements are very similar in the investigated Co-based and Ni-based superalloys. By interpreting the local chemical composition from EPMA with the structure map, we effectively unite the set of element distribution maps to compound maps with very good contrast of the dendritic microstructure. The resulting compound maps of the microstructure in terms of average band filling and atomic-size difference explain the formation of topologically close-packed phases in the interdendritic regions. We identify B2, C14, and D024 precipitates with chemical compositions that are in line with the structure map.

Convergence of an analytic bond-order potential for collinear magnetism in Fe

Analytic bond-order potentials (BOPs) for magnetic transition metals are applied for pure iron as described by an orthogonal d-valent tight-binding (TB) model. Explicit analytic equations for the gradients of the binding energy with respect to the Hamiltonian on-site levels are presented, and are then used to minimize the energy with respect to the magnetic moments, which is equivalent to a TB self-consistency scheme. These gradients are also used to calculate the exact forces, consistent with the energy, necessary for efficient relaxations and molecular dynamics. The Jackson kernel is used to remove unphysical negative densities of states, and approximations for the asymptotic recursion coefficients are examined. BOP, TB and density functional theory results are compared for a range of bulk and defect magnetic structures. The BOP energies and magnetic moments for bulk structures are shown to converge with increasing numbers of moments, with nine moments sufficient for a quantitative comparison of structural energy differences. The formation energies of simple defects such as the monovacancies and divacancies also converge rapidly. Other physical quantities, such as the position of the high-spin to low-spin transition in ferromagnetic fcc (face centred cubic) iron, surface peaks in the local density of states, the elastic constants and the formation energies of the self-interstitial atom defects, require higher moments for convergence.

Analytic bond-order potentials for the bcc refractory metals Nb, Ta, Mo and W.

Bond-order potentials (BOPs) are based on the tight-binding approximation for determining the energy of a system of interacting atoms. The bond energy and forces are computed analytically within the formalism of the analytic BOPs. Here we present parametrizations of the analytic BOPs for the bcc refractory metals Nb, Ta, Mo and W. The parametrizations are optimized for the equilibrium bcc structure and tested for atomic environments far from equilibrium that had not been included in the fitting procedure. These tests include structural energy differences for competing crystal structures; tetragonal, trigonal, hexagonal and orthorhombic deformation paths; formation energies of point defects as well as phonon dispersion relations. Our tests show good agreement with available experimental and theoretical data. In practice, we obtain the energetic ordering of vacancy, [1 1 1], [1 1 0], and [1 0 0] self-interstitial atom in agreement with density functional theory calculations.

Oxygen activity and peroxide formation as charge compensation mechanisms in Li2MnO3

In the search for high energy density battery materials, over-lithiated transition metal oxides have attracted the attention of many researchers worldwide. There is, however, no consensus regarding the underlying mechanisms that give rise to the large capacities and also cause the electrochemical degradation upon cycling. As a key component and prototype phase, Li2MnO3 is investigated using density functional theory. Our calculations show that hole doping into the oxygen bands is the primary charge compensation mechanism in the first stage of delithiation. Upon further delithiation, there is an energetic driving force for peroxide formation with an optimal number of peroxide dimers that is predicted as a function of lithium concentration. Unlike the defect-free phases, the peroxide structures are highly stable, which leads to two competing mechanisms for charge compensation: (i) oxygen loss and densification at the surface and (ii) peroxide formation in the bulk. Our results show that both have a detrimental effect on the electrochemical performance and therefore the stabilization of oxygen in the crystal lattice is vital for the development of high energy cathode materials. The insights into the origin and implications of peroxide formation open the door for a more profound understanding of the degradation mechanism and how to counteract it.

Complexity analysis of simulations with analytic bond-order potentials

The modeling of materials at the atomistic level with interatomic potentials requires a reliable description of different bonding situations and relevant system properties. For this purpose, analytic bond-order potentials (BOPs) provide a systematic and robust approximation to density functional theory (DFT) and tight binding (TB) calculations at reasonable computational cost. This paper presents a formal analysis of the computational complexity of analytic BOP simulations, based on a detailed assessment of the most computationally intensive parts. Different implementation algorithms are presented alongside with optimizations for efficient numerical processing. The theoretical complexity study is complemented by systematic benchmarks of the scalability of the algorithms with increasing system size and accuracy level of the BOP approximation. Both approaches demonstrate that the computation of atomic forces in analytic BOPs can be performed with a similar scaling as the computation of atomic energies.

Efficient parallelization of analytic bond-order potentials for large-scale atomistic simulations

Abstract Analytic bond-order potentials (BOPs) provide a way to compute atomistic properties with controllable accuracy. For large-scale computations of heterogeneous compounds at the atomistic level, both the computational efficiency and memory demand of BOP implementations have to be optimized. Since the evaluation of BOPs is a local operation within a finite environment, the parallelization concepts known from short-range interacting particle simulations can be applied to improve the performance of these simulations. In this work, several efficient parallelization methods for BOPs that use three-dimensional domain decomposition schemes are described. The schemes are implemented into the bond-order potential code BOPfox, and their performance is measured in a series of benchmarks. Systems of up to several millions of atoms are simulated on a high performance computing system, and parallel scaling is demonstrated for up to thousands of processors.

Role of strain relaxation during different stages of InAs quantum dot growth

Recent experiments suggest that InAs quantum dots grown on GaAs (001) undergo a shape transition during growth from “hut” to “dome”‐like shapes, similar to Ge quantum dots on Si. From a thermodynamic point of view, quantum dot formation is governed by the energetic balance between the energy gain due to strain relief and the energy cost due to formation of quantum dot side facets and edges. In order to account for both contributions, we have developed a carefully parametrized bond‐order potential. Its analytical form follows the previous suggestions by Abell and Tersoff, but the newly determined parameters have been fitted to reproduce the elastic constants as well as properties of both GaAs and InAs low‐index surface reconstructions obtained from density‐functional theory calculations. The potential describes the elastic constants with less than 10 % deviation and the considered surface energies within 10 meV/A2. The results of our calculations are helpful in analysing the energetics of different experim...

Finite-temperature property-maps of Li–Mn–Ni–O cathode materials from ab initio calculations

We report first-principles calculations for determining the phase relationships in multi-component cathode materials. We investigate the effect of delithiation on the phase stability, chemical potential, and open circuit voltage for a selection of cathode materials based on Li–Mn–Ni oxides at various temperatures. Entropic contributions are included by calculating the phonon frequencies in the harmonic approximation. The open circuit voltage in multi-component systems is estimated by a convex hull approach. We confirm that spinel-like phases are predominant during the charging process of layered Li–Mn–O cathode materials and that the addition of Ni reduces the spinel content. The analysis of phase stability upon delithiation suggests that the Li2MnO3 component in the Li2MnO3·Li(Mn,Ni)O2 electrode material should not exceed 60% and that the amount of Ni in the LiMnO2 component should be above 40 at% for minimizing spinel-type phase formation and minimizing oxygen formation. Using the computed structural stability at room temperature, we derive property maps for the design of Li–Mn–Ni–O cathode materials.

Strain field calculations of quantum dots — a comparison study of two methods

The elastic strain field plays a crucial role during the self‐organized growth of semiconductor quantum dot structures in the Stranski‐Krastanov growth mode. Several theoretical methods have been developed for calculating the strain field of these lattice‐mismatched systems. In this report we present a study exemplarily comparing an atomistic approach and calculations using elasticity theory. Features, limitations and selected possible applications of both approaches are discussed.