0000000000021989
AUTHOR
Maija M. Kuklja
showing 20 related works from this author
Defects in yttrium aluminium perovskite and garnet crystals: atomistic study
2000
Native and impurity point defects in both yttrium aluminium perovskite (YAP) and garnet (YAG) crystals are studied in the framework of the pair-potential approximation coupled with the shell model description of the lattice ions. The calculated formation energies for native defects suggest that the antisite disorder is preferred over the Frenkel and Schottky-like disorder in both YAP and YAG. The calculated values of the distortion caused by the antisite YAl x in the lattice turn out to be in an excellent agreement with the EXAFS measurements. In non-stoichiometric compounds, the calculated reaction energies indicate that excess Y2 O3 or Al2 O3 is most likely to be accommodated by the forma…
Quantum chemical calculations of the electron center diffusion in MgO crystals
1996
Large-scale quantum chemical simulations of the diffusion hops of empty cation and anion vacancies, as well as F + and F centers in MgO crystals have been done. The atomic configurations for 224-site cluster and charge density distribution are analyzed for the equilibrium and saddle-point configurations during the defect hops. The relevant activation energy for diffusion increases monotonically in the series V a → F + → F center.
Quantum chemical simulations of the optical properties and diffusion of electron centres in mgo crystals
1996
Semiempirical quantum chemical simulations have been undertaken to obtain the self-consistent atomic and electronic structure of the two basic electron defects in MgO crystals: F+ and F centres (one and two electrons trapped by an 0 vacancy, V,). The calculated absorption and luminescence energies agree well with the experimental data; the excited states of both defects are found to be essentially delocalised over nearest-neighbour cations. The activation energy for diffusion is found to increase monotonically in a series V, --f F+ --f F centre (2.50 eV, 2.72 eV and 3.13 eV, respectively).
First principles calculations of oxygen vacancy formation and migration in mixed conducting Ba0.5Sr0.5Co1−yFeyO3−δ perovskites
2011
Abstract First-principles supercell calculations of oxygen vacancies in the Ba 0.5 Sr 0.5 Co 1− y Fe y O 3− δ (BSCF) perovskites are presented. The density of states is determined for different iron content and oxygen vacancy concentrations, and the characteristic differences for Co and Fe are discussed. We analyze the dependences of the defect (oxygen vacancy) formation and migration energies on the Fe content and compare the calculated properties with those of related LaCoO 3 and LaFeO 3 perovskites.
Surface termination effects on the oxygen reduction reaction rate at fuel cell cathodes
2018
This research was partly funded by the Latvian project IMIS2 with the computer resources provided by the High Performance Computing Centre Stuttgart (HLRS) (Project DEFTD 12939). The authors thank D. Gryaznov for fruitful discussions and M. Sokolov for technical assistance. MMK is grateful to the Office of the Director of National Science Foundation for support under the Independent Research and Development program. The ndings, conclusions, and recommendations expressed in this material are those of the authors and do not necessarily reect the views of NSF and other funding agencies.
First principles calculations of (Ba,Sr)(Co,Fe)O3−δ structural stability
2013
Abstract First principles total-energy calculations of an ideal BSCF perovskite-type solid solution, the crystal containing basic point defects, and a set of relevant solid–solid solutions are presented. Our DFT modeling of defects (Frenkel, Schottky and cation exchange) and disordering in the BSCF perovskites reveals that the material tends to decompose at relatively low temperatures into a mixture of new perovskite and oxide phases. These new phases are likely to appear at grain boundaries and surface interfaces. This instability is predicted to negate advantages of fast oxygen transport chemistry and impede the applicability of BSCF-based SOFC and ceramic permeation membranes. We discuss…
Diffusion of point defects in shocked molecular crystals
2005
The dynamic response of a molecular crystal containing defects to shock wave loading is modeled and the resulting diffusion of point defects is simulated. It is shown that diffusion proceeds not only via the stress assisted diffusion, which is point defect diffusion in a stress field, also known as the Gorsky effect, but also through defect diffusion in the field of inertial forces. The method for modeling diffusion of point defects in shocked solids is developed. It is shown that diffusion in the inertial field significantly exceeds the stress diffusion in organic molecular crystals. Interplay between stress-assisted and inertial diffusion leads to the separation of light particles from he…
Defect Calculations for Yttrium Aluminum Perovskite and Garnet Crystals
2000
Native and impurity point defects in both Yttrium Aluminum Perovskite and Garnet crystals are studied in the framework of the pair-potential and the shell model approximations. The calculated formation energies for native defects suggest that the antisite disorder is preferred over the Frenkel and Schottky-like disorder in both YAP and YAG. In non-stoichiometric compounds, the calculated reaction energies indicate that excess of Y2O3 or Al2O3 is, most likely, to be accommodated by the formation of antisites rather than vacancies or interstitials in the lattice. Enthalpies of the reactions for impurity (Ca2+, Mg2+, Sr2+, Ba2+, Cr3+, Fe3+, Nd3+, Si4+) incorporation into both YAP and YAG latti…
The Structural Disorder and Lattice Stability of (Ba,Sr)(Co,Fe)O3 Complex Perovskites
2011
The structural disorder and lattice stability of complex perovskite (Ba,Sr)(Co,Fe)O3, a promising cathode material for solid oxide fuel cells and oxygen permeation membranes, is explored by means of first principles DFT calculations. It is predicted that Ba and Sr ions easily exchange their lattice positions (A-cation disorder) similarly to Co and Fe ions (B-cation disorder). The cation antisite defects (exchange of A- and B-type cations) also have the low formation energy. The BSCF is predicted to exist in an equilibrium mixture of several phases and can decompose exothermically into the Ba- and Co-rich hexagonal (Ba,Sr)CoO3 and Sr- and Fe-rich cubic (Ba,Sr)FeO3 perovskites.
The Intrinsic Defects, Disordering, and Structural Stability of BaxSr1–xCoyFe1–yO3−δ Perovskite Solid Solutions
2012
First principles density functional theory modeling of point defects and structural disordering in BaxSr1–xCoyFe1–yO3−δ (BSCF) perovskites reveals that the material tends to decompose at low temperatures into a mixture of cubic and hexagonal perovskite and/or oxide phases. Special attention is paid to elucidating the effects of oxygen nonstoichiometry on cubic and hexagonal phase stability, decomposition energies, and oxygen vacancy formation energies. The observed lattice instability is likely to negate the advantages of the fast oxygen transport chemistry and impede the applicability of BSCF in solid oxide fuel cells and oxygen separation ceramic membranes. The general methodology present…
Semi-empirical simulations of F-center diffusion in KCl crystals
1997
Abstract The semi-empirical method and 224 atom quantum clusters were used for calculating the activation energy for diffusion of cation and anion vacancies and F-centers in KCl crystals. The relevant activation energies of 1.19 eV, 1.44 eV and 1.64 eV, respectively agree well with the experimental data.
(Invited) The Effect of (La,Sr)MnO 3 Cathode Surface Termination on Its Electronic Structure
2017
La1-xSrxMnO3 (LSM) was one of the first perovskites used as SOFC cathode material. Its (001) surface has two possible terminations, LaSrO and MnO2, with quite different properties and oxygen reduction efficiencies. To avoid effects of surface polarity and the dipole moment across the material, symmetric non-stoichiometric slabs are commonly used in theoretical calculations with identical terminating planes on its both sides. We analyzed the dependence of the electronic structure (density of states) and charge distribution (effective atomic charges and chemical bond covalency) on the slab termination and Mn ion oxidation state (controlled by the Sr content and slab nonstoichiometry).
First-principles modelling of complex perovskite (Ba1-xSrx)(Co1-yFey)O3-δ for solid oxide fuel cell and gas separation membrane applications
2010
The results of the first principles spin-polarized DFT calculations of the atomic and electronic structure of a complex perovskite (Ba1-xSrx)(Co1-yFey)O3-δ (BSCF) used as a cathode material for solid oxide fuel cells (SOFC) and gas separation membranes are presented and discussed. The formation energies of oxygen vacancies are found to be considerably smaller than in other magnetic perovskites, e.g. (La,Sr)MnO3, which explains the experimentally observed strong deviation of this material from stoichiometry. The presence of oxygen vacancies induces a local charge redistribution, associated with the local lattice perturbation, and expansion of the equilibrium volume, in line with the experime…
Radiation defects in complex perovskite solid solutions
2014
Abstract First principles density functional theory (DFT) based modeling is performed to explore formation energies of a series of point cation and oxygen defects, Frenkel and Schottky disorder, as well as structural disorder in Ba1−xSrxCo1−yFeyO3−δ (BSCF) perovskite solid solutions. The results are compared with previous studies on a prototype SrTiO3 perovskite. It is shown that BSCF permits accommodation of a high concentration of defects and cation clusters but not antisite defects.
Theoretical analysis of hole self-trapping in ionic solids: Application to the KCl crystal.
1993
A method for the calculation of the hole self-trapping (ST) energy in ionic crystals is proposed. It combines model-Hamiltonian and quantum-chemical approaches. An artificial path for the ST process has been suggested containing (a) a free hole not interacting with the lattice vibrations; (b) a free-hole wave packet localized in a small crystal volume in the form of the real ST state, all crystal ions being in their perfect lattice positions; (c) the final ST state of the hole, accompanied with a corresponding lattice relaxation, including strong displacements of ions belonging to the hole region. Some intermediate states might be adopted between (a) and (b) in order to simplify the calcula…
Formation and migration of oxygen vacancies in La1−xSrxCo1−yFeyO3−δperovskites: insight from ab initio calculations and comparison with Ba1−xSrxCo1−y…
2013
The formation and migration of oxygen vacancies in the series of (La,Sr)(Co,Fe)O3−δ perovskites, which can be used as mixed conducting SOFC cathode materials and oxygen permeation membranes, are explored in detail by means of first principles density functional calculations. Structure distortions, charge redistributions and transition state energies during the oxygen ion migration are obtained and analyzed. Both the overall chemical composition and vacancy formation energy are found to have only a small impact on the migration barrier; it is rather the local cation configuration which affects the barrier. The electron charge transfer from the migrating O ion towards the transition metal ion…
Energy Conversion: Solid Oxide Fuel Cells: First-Principles Modeling of Elementary Processes
2013
Fuel cells are electrochemical devices that directly transform the chemical free energy of combustion (e.g., H2 + O2 and CHx + O2) into electrical energy. The avoidance of a thermal detour guarantees high theoretical efficiency. As far as the temperature regimes are concerned, we distinguish between high temperature ceramic fuel cells, intermediate-temperature fuel cells, and low temperature (i.e., only slightly above room temperature) fuel cells. The high temperature fuel cells are usually based on oxide components (ternary transition metal oxides as cathodes, Ni or Cu cermets as anodes, and acceptor-doped zirconia or ceria as electrolytes). The high temperature necessary for ion conductio…
First Principles Calculations of Oxygen Vacancy Formation and Migration in Ba1−xSrxCo1−yFeyO3−δPerovskites
2011
Based on first principles DFT calculations, we analyze oxygen vacancy formation and migration energies as a function of chemical composition in complex multicomponent (Ba,Sr)(Co,Fe)O3−δ perovskites which are candidate materials for SOFC cathodes and permeation membranes. The atomic relaxation, electronic charge redistribution and energies of the transition states of oxygen migration are compared for several perovskites to elucidate the atomistic reason for the exceptionally low migration barrier in Ba0.5Sr0.5Co0.8Fe0.2O3−δ that was previously determined experimentally. The critical comparison of Ba1−xSrxCo1−yFeyO3−δ perovskites with different cation compositions and arrangements shows that …
Combined theoretical and experimental analysis of processes determining cathode performance in solid oxide fuel cells
2013
Solid oxide fuel cells (SOFC) are under intensive investigation since the 1980's as these devices open the way for ecologically clean direct conversion of the chemical energy into electricity, avoiding the efficiency limitation by Carnot's cycle for thermochemical conversion. However, the practical development of SOFC faces a number of unresolved fundamental problems, in particular concerning the kinetics of the electrode reactions, especially oxygen reduction reaction. We review recent experimental and theoretical achievements in the current understanding of the cathode performance by exploring and comparing mostly three materials: (La,Sr)MnO3 (LSM), (La,Sr)(Co,Fe)O3 (LSCF) and (Ba,Sr)(Co,…
Ab initioand semiempirical calculations ofH−centers in MgO crystals
1999
The atomic and electronic structure of ${\mathrm{H}}^{\ensuremath{-}}$ ions substituting for ${\mathrm{O}}^{2\ensuremath{-}}$ ions in regular sites in MgO crystals are calculated using an ab initio Hartree-Fock (HF) cluster approach and its semiempirical version, intermediate neglect of the differential overlap. The theoretical optical absorption energy is predicted to be 10 eV, which is supported by analysis of experimental data for the ${\mathrm{H}}^{\ensuremath{-}}$ centers in a series of ionic crystals. The HF simulations of ${\mathrm{H}}^{\ensuremath{-}}$ ion diffusion via direct interstitial hops along the [100] axis predict an activation energy of about 3 eV.