03 Fakultät Chemie
Permanent URI for this collectionhttps://elib.uni-stuttgart.de/handle/11682/4
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Item Open Access Efficient approach to compute melting properties fully from ab initio with application to Cu(2017) Zhu, Li-Fang; Grabowski, Blazej; Neugebauer, JörgApplying thermodynamic integration within an ab initio-based free-energy approach is a state-of-the-art method to calculate melting points of materials. However, the high computational cost and the reliance on a good reference system for calculating the liquid free energy have so far hindered a general application. To overcome these challenges, we propose the two-optimized references thermodynamic integration using Langevin dynamics (TOR-TILD) method in this work by extending the two-stage upsampled thermodynamic integration using Langevin dynamics (TU-TILD) method, which has been originally developed to obtain anharmonic free energies of solids, to the calculation of liquid free energies. The core idea of TOR-TILD is to fit two empirical potentials to the energies from density functional theory based molecular dynamics runs for the solid and the liquid phase and to use these potentials as reference systems for thermodynamic integration. Because the empirical potentials closely reproduce the ab initio system in the relevant part of the phase space the convergence of the thermodynamic integration is very rapid. Therefore, the proposed approach improves significantly the computational efficiency while preserving the required accuracy. As a test case, we apply TOR-TILD to fcc Cu computing not only the melting point but various other melting properties, such as the entropy and enthalpy of fusion and the volume change upon melting. The generalized gradient approximation (GGA) with the Perdew-Burke-Ernzerhof (PBE) exchange-correlation functional and the local-density approximation (LDA) are used. Using both functionals gives a reliable ab initio confidence interval for the melting point, the enthalpy of fusion, and entropy of fusion.Item Open Access Analytical energy gradients for open-shell local second-order Møller-Plesset perturbation theory and applications to large molecules(2018) Dornbach, Mark; Werner, Hans-Joachim (Prof. Dr.)Item Open Access Migration mechanisms of a faceted grain boundary(2018) Hadian, Raheleh; Grabowski, Blazej; Finnis, Michael W.; Neugebauer, JörgWe report molecular dynamics simulations and their analysis for a mixed tilt and twist grain boundary vicinal to the Σ7 symmetric tilt boundary of the type {123} in aluminum. When minimized in energy at 0K, a grain boundary of this type exhibits nanofacets that contain kinks. We observe that at higher temperatures of migration simulations, given extended annealing times, it is energetically favorable for these nanofacets to coalesce into a large terrace-facet structure. Therefore, we initiate the simulations from such a structure and study as a function of applied driving force and temperature how the boundary migrates. We find the migration of a faceted boundary can be described in terms of the flow of steps. The migration is dominated at lower driving force by the collective motion of the steps incorporated in the facet, and at higher driving forces by the step detachment from the terrace-facet junction and propagation of steps across the terraces. The velocity of steps on terraces is faster than their velocity when incorporated in the facet, and very much faster than the velocity of the facet profile itself, which is almost stationary. A simple kinetic Monte Carlo model matches the broad kinematic features revealed by the molecular dynamics. Since the mechanisms seem likely to be very general on kinked grain-boundary planes, the step-flow description is a promising approach to more quantitative modeling of general grain boundaries.Item Open Access Ab initio based method to study structural phase transitions in dynamically unstable crystals, with new insights on the β to ω transformation in titanium(2019) Korbmacher, Dominique; Glensk, Albert; Duff, Andrew Ian; Finnis, Michael W.; Grabowski, Blazej; Neugebauer, JörgWe present an approach that enables an efficient and accurate study of dynamically unstable crystals over the full temperature range. The approach is based on an interatomic potential fitted to ab initio molecular dynamics energies for both the high- and low-temperature stable phases. We verify by comparison to explicit ab initio simulations that such a bespoke potential, for which we use here the functional form of the embedded atom method, provides accurate transformation temperatures and atomistic features of the transformation. The accuracy of the potential makes it an ideal tool to study the important impact of finite size and finite time effects. We apply our approach to the dynamically unstable β (bcc) titanium phase and study in detail the transformation to the low-temperature stable hexagonal ω phase. We find a large set of previously unreported linear-chain disordered (LCD) structures made up of three types of [111]β linear-chain defects that exhibit randomly disordered arrangements in the (111)β plane.Item Open Access Phonon lifetimes throughout the Brillouin zone at elevated temperatures from experiment and ab Initio(2019) Glensk, Albert; Grabowski, Blazej; Hickel, Tilmann; Neugebauer, Jörg; Neuhaus, Jürgen; Hradil, Klaudia; Petry, Winfried; Leitner, MichaelWe obtain phonon lifetimes in aluminium by inelastic neutron scattering experiments, by ab initio molecular dynamics, and by perturbation theory. At elevated temperatures significant discrepancies are found between experiment and perturbation theory, which disappear when using molecular dynamics due to the inclusion of full anharmonicity and the correct treatment of the multiphonon background. We show that multiple-site interactions are small and that local pairwise anharmonicity dominates phonon-phonon interactions, which permits an efficient computation of phonon lifetimes.Item Open Access Impact of asymmetric martensite and austenite nucleation and growth behavior on the phase stability and hysteresis of freestanding shape-memory nanoparticles(2018) Ko, Won-Seok; Grabowski, Blazej; Neugebauer, JörgMartensitic transformations in nanoscaled shape-memory alloys exhibit characteristic features absent for the bulk counterparts. Detailed understanding is required for applications in micro- and nanoelectromechanical systems, and experimental limitations render atomistic simulation an important complementary approach. Using a recently developed, accurate potential we investigate the phase transformation in freestanding Ni-Ti shape-memory nanoparticles with molecular-dynamics simulations. The results confirm that the decrease in the transformation temperature with decreasing particle size is correlated with an overstabilization of the austenitic surface energy over the martensitic surface energy. However, a detailed atomistic analysis of the nucleation and growth behavior reveals an unexpected difference in the mechanisms determining the austenite finish and martensite start temperature. While the austenite finish temperature is directly affected by a contribution of the surface energy difference, the martensite start temperature is mostly affected by the transformation strain, contrary to general expectations. This insight not only explains the reduced transformation temperature but also the reduced thermal hysteresis in freestanding nanoparticles.Item Open Access Spectroscopic investigations of the magnetic anisotropy of lanthanide- and cobalt-based molecular nanomagnets(2016) Rechkemmer, Yvonne; Slageren, Joris van (Prof. Dr.)Single-molecule magnets are metal complexes exhibiting an energy barrier for spin reversal, leading to magnetic bistability and slow relaxation of the magnetization. Their potential for practical applications such as high-density magnetic data storage was recognized early on and with the goal of achieving high energy barriers, different kinds of single-molecule magnets have been synthesized. The quadratic dependence of the barrier height on the spin motivated chemists to synthesize metal complexes with very high total spins; however, with limited success. It was shown that high spins come along with low anisotropies and increased interest thus focused on the synthesis and investigation of (mononuclear) complexes of highly anisotropic metal centers, e.g. lanthanide or cobalt complexes. Although rather high energy barriers can be achieved in such systems, practical application remains problematic and has not been realized yet. Reasons are for example the lack of rational design criteria and the complex interplay of different magnetic relaxation pathways. The aim of this work was therefore the comprehensive magnetic and spectroscopic investigation of selected molecular lanthanide and cobalt compounds in order to obtain a deeper insight into the correlation of molecular and electronic structures as well as the corresponding magnetic properties. The applied spectroscopic methods included electron paramagnetic resonance spectroscopy, far-infrared spectroscopy and optical methods. Special emphasis was placed on magnetic circular dichroism (MCD) spectroscopy, which served as a main tool for electronic structure determination. However, since the MCD-spectrometer was not part of the available experimental equipment at the University of Stuttgart, its design, setup and characterization were the first part of this work. In the further course of this work MCD-spectroscopy was employed for the electronic structure determination of selected lanthanide and cobalt compounds. The studied lanthanide compounds were literature-known molecular tetra-carbonates of erbium (1-Er) and dysprosium (1-Dy). Detailed magnetometric studies showed that both 1-Er and 1-Dy are field-induced single-molecule magnets; however, 1-Er and 1-Dy show significant differences in their magnetic relaxation behavior. The magnetic studies were complemented by detailed spectroscopic investigations.The combination of far-infrared-, luminescence- and MCD-spectroscopy allowed for the experimental determination of 48 energy levels for 1-Er and 55 levels for 1-Dy, which built the foundation for the subsequent crystal field analysis and electronic structure determination. In addition, the results of EPR-spectroscopic studies were used for fine-tuning and verifying the respectively determined crystal field parameters. Calculating the magnetic dipole strengths for transitions between the relevant states led to a quantitative understanding of the magnetic relaxation pathways. Besides the investigation of lanthanide compounds, this thesis deals with two classes of cobalt complexes. The first class comprises mononuclear complexes in which one Co(II) ion is ligated by the nitrogen donors of two doubly deprotonated 1,2-bis(methanesulfonamido)-benzene-ligands. Rather acute N-Co-N bite angles indicate strong deviations from ideal tetrahedral symmetry. The static magnetic properties hint at very high energy barriers for spin reversal and with the help of far-infrared spectroscopy, largely negative axial zero-field splitting parameters were determined. The corresponding energy barriers belong to the highest ever reported for 3d-transition metal complexes and investigating the dynamic magnetic properties confirmed single-molecule magnet behavior. The unique magnetic properties were fully explained by analyzing spectroscopic results. The MCD-spectra showed intense signals that were assigned to spin-allowed d-d-transitions. Subsequent crystal field analysis revealed that the strong axial crystal field generated by the ligands leads to a large splitting of the electronic terms and thus in turn to a relatively small energy gap between the electronic ground state and the first excited state. The resulting increase in second-order spin-orbit coupling explains the high energy barriers observed in the studied complexes. The second class of cobalt compounds studied in this work included dimers of distorted octahedrally coordinated Co(II) ions bridged by symmetrical or asymmetrical quinone based bridging ligands. The main focus of investigation lay on the impact of the bridging ligand on the magnetic coupling between the cobalt centers. Thus, the magnetic properties of the complexes were studied with the help of static susceptibility and magnetization measurements and analyzed by means of different models. Depending on the bridging ligand, different signs for the exchange coupling constants were found. The varying signs can be explained by different relative contributions of possible exchange paths, influenced by the different substituents at the bridging ligands or slight geometry differences. The observations indicate that electron withdrawing substituents favor ferromagnetic couplings, which are preferred in the context of molecular magnetism. All in all, it can be concluded that this work provides a contribution to the deeper understanding of the features relevant for single-molecule magnets. The electronic structure determination for selected lanthanide and cobalt complexes applying advanced magnetometric and spectroscopic techniques not only led to an understanding of the static and dynamic magnetic properties but also allowed for the development of design criteria and new approaches for improved single-molecule magnets in the future.Item Open Access k-Space magnetism as the origin of superconductivity(2018) Krüger, EkkehardThe nonadiabatic Heisenberg model presents a nonadiabatic mechanism generating Cooper pairs in narrow, roughly half-filled "superconducting bands" of special symmetry. Here, I show that this mechanism may be understood as the outcome of a special spin structure in the reciprocal space, hereinafter referred to as "k-space magnetism". The presented picture permits a vivid depiction of this new mechanism highlighting the height similarity as well as the essential difference between the new nonadiabatic and the familiar Bardeen-Cooper-Schrieffer mechanism.Item Open Access Accurate electronic free energies of the 3d, 4d, and 5d transition metals at high temperatures(2017) Zhang, Xi; Grabowski, Blazej; Körmann, Fritz; Freysoldt, Christoph; Neugebauer, JörgFree energies of bulk materials are nowadays routinely computed by density functional theory. In particular for metals, electronic excitations can significantly contribute to the free energy. For an ideal static lattice, this contribution can be obtained at low computational cost, e.g., from the electronic density of states derived at T = 0 K or by utilizing the Sommerfeld approximation. The error introduced by these approximations at elevated temperatures is rarely known. The error arising from the ideal lattice approximation is likewise unexplored but computationally much more challenging to overcome. In order to shed light on these issues we have computed the electronic free energies for all 3d, 4d, and 5d transition elements on the ideal lattices of the bcc, fcc, and hcp structures using finite-temperature density-functional theory. For a subset of elements we have explored the impact of explicit thermal vibrations on the electronic free energies by using ab initio molecular dynamics simulations. We provide an analysis of the observed chemical trends in terms of the electronic density of states and the canonical d band model and quantify the errors in the approximate methods. The electronic contribution to the heat capacities and the corresponding errors due to the different approximations are studied as well.Item Open Access Novel X-ray lenses for direct and coherent imaging(2019) Sanli, Umut Tunca; Schütz, Gisela (Prof. Dr.)