Density functionals, Organometallic compounds, Oxides, Rare earth metals, Transition metals


Density Functional Theory (DFT) method is applied to study the crystal structure of transition metal and lanthanide oxides, as well as molecular magnetic complexes. DFT is a widely popular computational approach because it recasts a many-body problem of interacting electrons into an equivalent problem of non-interacting electrons, greatly reducing computational cost. We show that for certain structural properties like phase stability, lattice parameter and oxygen migration energetics pure DFT can give good agreement with experiments. But moving to more sensitive properties like spin state energetic certain modifications of standard DFT are needed. First we investigated mixed ionic-electronic conducting perovskite type oxides with a general formula ABO3 (where A =Ba, Sr, Ca and B = Co, Fe, Mn). These oxides often have high mobility of the oxygen vacancies and exhibit strong ionic conductivity. They are key materials that find use in several energy related applications, including solid oxide fuel cell (SOFC), sensors, oxygen separation membranes, and catalysts. Different cations and oxygen vacancies ordering are examined using plane wave pseudopotential density functional theory. We find that cations are completely disordered, whereas oxygen vacancies exhibit a strong trend for aggregation in L-shaped trimer and square tetramer structure. On the basis of our results, we suggest a new explanation for BSCF phase stability. Instead of linear vacancy ordering, which must take place before the phase transition into brownmillerite structure, the oxygen vacancies in BSCF prefer to form the finite clusters and preserve the disordered cubic structure. This structural feature could be found only in the first-principles simulations and cannot be explained by the effect of the ionic radii alone. In order to understand vacancy clustering and phase iv stability in oxygen-deficient barium strontium cobalt iron oxide (BSCF), we predict stability and activation energies for oxygen vacancy migration. Using symmetry constrained search and Nudged Elastic Band method, we characterize the transition states for an oxygen anion moving into a nearby oxygen vacancy site that is surrounded by different cations and find the activation energies to vary in the range 30-50 kJ/mol in good agreement with experimental data. Next we study spin alignments of single molecule magnets (SMM). SMMs are a class of polynuclear transition metal complexes, which characterized by a large spin ground state and considerable negative anisotropy. These properties lead to a barrier for the reversal of magnetization. For these reasons SMM are expected to be promising materials for molecular spintronics and quantum computing applications. To design SMM for quantum computation, we need to accurately predict their magnetic properties. The most important property is, Heisenberg exchange coupling constant (J). This constant appears in model Heisenberg Hamiltonian that can be written in general form as here Jij represents the coupling between the two magnetic centers i and j with the spin states Si and Sj. The positive J values indicate the ferromagnetic ground state and the negative ones indicate the antiferromagnetic ground state. We found pure DFT is not accurate enough to predict J values. We employ density functionals with a Hubbard U term that helps to counteract the unphysical delocalization of electrons due to errors in pure exchange-correlation functionals. Unlike most previous DFT+U studies, we calibrate U parameters for both metal and ligand atoms using five binuclear manganese complexes as the benchmarks. We note delocalization of the spin density onto acetate ligands due to π-back bonding, inverting spin-polarization of the Jiij −= ∑ S.S.JH v acetate oxygen atoms relative to that predicted from superexchange mechanism. This inversion may affect performance of the models assuming strict localization of the spins on magnetic centers for the complexes with bridging acetate ligands. Next, we apply DFT+U methodology for Mn12(mda) and Mn12(ada) complexes to calculate all six nearest neighbor Jij value. Our result shows both qualitative and quantitative agreement with experiments unlike other DFT studies. Using the optimized geometry of the ground spin state instead of less accurate experimental geometry was found to be crucial for this good agreement. The protocol tested in this study can be applied for the rational design of single-molecule magnets for molecular spintronics and quantum computing applications. Finally we apply hybrid DFT methodology to calculate geometrical parameters for cerium oxides. We review the experimental and computational studies on the cerium oxide nanoparticles, as well as stoichiometric phases of bulk ceria. Electroneutral and nonpolar pentalayers are identified as building blocks of type A sesqioxide structure. The idealized structure of the nanoparticles is described as dioxide covered by a single pentalayer of sesquioxide, which explains the exceptional stability of subsurface vacancies in nanoceria. The density functional theory (DFT) predictions of the lattice parameters and bulk moduli for the Ce(IV) and Ce(III) oxides at the hybrid DFT level are also presented. The calculated values for both compounds agree with experiment and allow to predict changes in the lattice parameter with decreasing size of the nanoparticles. The results validate hybrid DFT as a promising method for future study the structure of oxygen vacancies and catalytic properties of ceria nanoparticles.


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Graduation Date





Masunov, Artem E.


Doctor of Philosophy (Ph.D.)


College of Sciences










Release Date

April 2014

Length of Campus-only Access

3 years

Access Status

Doctoral Dissertation (Open Access)


Dissertations, Academic -- Sciences, Sciences -- Dissertations, Academic

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