Correlated Electronic Structure of Materials : Development and Application of Dynamical Mean Field Theory

Abstract: This thesis is dedicated to the development, implementation and application of a combination of Density Functional Theory and Dynamical Mean Field Theory. The resulting program is shown through several examples to be a powerful and flexible tool for calculating the electronic structure of strongly correlated materials. The main part of this work is focused on the development and implementation of three methods for solving the effective impurity model arising in the Dynamical Mean Field Theory: Hubbard-I approximation (HIA), Exact Diagonalization (ED), and Spin-Polarized T-matrix Fluctuation-exchange (SPTF). The Hubbard-I approximation is limited to systems where the hybridization between the 4f-orbitals and the rest of the material can be completely neglected, and can therefore not capture any Kondo physics. It has been used to study the atomic-like multiplet spectrum of the strongly localized 4f-electrons in the Lanthanide compounds YbInCu4, YbB12, Yb2Pd2Sn, YbPd2Sn, SmB6, SmSn3, and SmCo5. The calculated spectral properties are shown to be in excellent agreement with experimental direct and inverse photoemission data, clearly affirming the applicability of the Hubbard-I approximation for this class of systems if we are not focusing on Kondo physics. Full self-consistence in both self-energy and electron density is shown to be of key importance in the extraction of the magnetic properties of the hard permanent magnet SmCo5. The Exact Diagonalization solver is implemented as an extension of the Hubbard-I approximation. It takes into account a significant part of the hybridization between the correlated atom and the host through the use of a few effective bath orbitals. This approach has been applied to the long-standing problem of the electronic structure of NiO, CoO, FeO, and MnO. The resulting spectral densities are favorably compared to photoemission spectroscopy. Apart from predicting the correct spectral properties, the Exact Diagonalization solver also provides full access to the many-body density operator. This feature is used to make an in-depth investigation of the correlations in the electronic structure, and two measures of the quantum entanglement of the many-body ground-states are presented. It is shown that CoO possesses the most intricate entanglement properties, due to a competition between crystal field effects and Coulomb interaction, and such a mechanism likely carries over to several classes of correlated electron systems. The Exact Diagonalization solver has also been applied to the prototypical dilute magnetic semiconductor Mn doped GaAs, a material of great importance in the study of future spintronics applications. The problem of Fe impurities in Cs has been used to study the dependence of the spectral properties on the local environment. Finally, the Spin-polarized T-matrix Fluctuation-exchange solver has been implemented and applied to more delocalized electron systems where the effective impurity problem can be solved as a perturbation with respect to the strength of the local Coulomb interaction. This approach has been used to study the magnetic and spectral properties of the late transition metals, Fe, Co and Ni, and NiS.