S. Yu. Ezhov

Bio: S. Yu. Ezhov is an academic researcher from Russian Academy of Sciences. The author has contributed to research in topics: Electronic band structure & Magnetic field. The author has an hindex of 5, co-authored 5 publications receiving 797 citations.

Intermediate-spin state and properties of LaCoO3.

Abstract: The electronic structure of the perovskite ${\mathrm{LaCoO}}_{3}$ for different spin states of Co ions was calculated in the local-density approximation LDA+U approach The ground state is found to be a nonmagnetic insulator with Co ions in a low-spin state Somewhat higher in energy, we find two intermediate-spin states followed by a high-spin state at significantly higher energy The calculations show that Co 3d states of ${\mathit{t}}_{2\mathit{g}}$ symmetry form narrow bands which could easily localize, while ${\mathit{e}}_{\mathit{g}}$ orbitals, due to their strong hybridization with the oxygen 2p states, form a broad \ensuremath{\sigma}* band With temperature variation which is simulated by a corresponding change of the lattice parameters, a transition from the low- to intermediate-spin state occurs This intermediate-spin (occupation ${\mathit{t}}_{2\mathit{g}}^{5}$${\mathit{e}}_{\mathit{g}}^{1}$) can develop an orbital ordering which can account for the nonmetallic nature of ${\mathrm{LaCoO}}_{3}$ at 90 KT500 K Possible explanations of the magnetic behavior and gradual insulator-metal transition are suggested \textcopyright{} 1996 The American Physical Society

Orbital occupation, local spin, and exchange interactions in V2O3

Abstract: We present the results of an LDA and LDA+U band structure study of the monoclinic and the corundum phases of V2O3 and argue that the most prominent (spin 1/2) models used to describe the semiconductor metal transition are not valid. Contrary to the generally accepted assumptions we find that the large on site Coulomb and exchange interactions result in a total local spin of 1 rather than 1/2 and especially an orbital occupation which removes the orbital degeneracies and the freedom for orbital ordering. The calculated exchange interaction parameters lead to a magnetic structure consistent with experiment again without the need of orbital ordering. While the low-temperature monoclinic distortion of the corundum crystal structure produces a very small effect on electronic structure of v2o3, the change of magnetic order leads to drastic differences in band widths and band gaps. The low temperature monoclinic phase clearly favors the experimentally observed magnetic structure, but calculations for corundum crystal structure gave two consistent sets of exchange interaction parameters with nearly degenerate total energies suggesting a kind of frustration in the paramagnetic phase. These results strongly suggest that the phase transitions in V2O3 which is so often quoted as the example of a S=1/2 Mott Hubbard system have a different origin. So back to the drawing board!

Singlet semiconductor to ferromagnetic metal transition in FeSi.

Abstract: Adding the local Coulomb repulsion to the local density approximation, the so-called $\mathrm{LDA}+U$ scheme, leads us to predict a first order transition from a singlet semiconductor to ferromagnetic metal in FeSi with increasing magnetic field. Extensions to finite temperature lead to the interpretation that the anomalous behavior at room temperature and zero field arises from proximity to the critical point of this transition. This critical point at a finite field may be accessible in currently available magnetic fields.

Orbital polarization in LiVO2 and NaTiO2

Abstract: We present a band structure study of orbital polarization and ordering in the two-dimensional triangular-lattice transition metal compounds LiVO2 and NaTiO2. It is found that while in NaTiO2 the degeneracy of t2g orbitals is lifted due to the trigonal symmetry of the crystal and the strong on-site Coulomb interaction, in LiVO2 orbital degeneracy remains and orbital ordering corresponding to the trimerization of the two-dimensional lattice develops.

Singlet and triplet doped-hole configurations in La 2 Cu 0.5 Li 0.5 O 4

Abstract: The ordered alloy La_2Li_{0.5}Cu_{0.5}O_4 is found to be a band insulator in local density approximation (LDA) calculations with the unoccupied conduction band having predominantly d_{x^2-y^2}-symmetry and substantial weight in O 2p-orbitals. This is equivalent to a predominant local singlet configuration d^9L or a low spin Cu^{3+}-ion with both holes in orbits having d_{x^2-y^2}-symmetry, i.e. Zhang-Rice singlets. A fairly modest reduction of the apical Cu-O bondlength is sufficient to stabilize a high spin triplet Cu^{3+}-ionic configuration with holes in both d_{x^2-y^2} and d_{3z^2-r^2} orbits in LDA + U calculations. This leads us to identify the low energy triplet excitation found in NQR studies by Yoshinari et al. as a local high spin Cu^{3+} -ionic configuration accompanied by a substantial reduction of the apical Cu-O separation, i.e. a anti-Jahn-Teller triplet polaron.

First-principles calculations of the electronic structure and spectra of strongly correlated systems: the LDA+ U method

Abstract: The generalization of the Local Density Approximation (LDA) method for the systems with strong Coulomb correlations is presented which gives a correct description of the Mott insulators. The LDA+U method is based on the model hamiltonian approach and allows to take into account the non-sphericity of the Coulomb and exchange interactions. parameters. Orbital-dependent LDA+U potential gives correct orbital polarization and corresponding Jahn-Teller distortion. To calculate the spectra of the strongly correlated systems the impurity Anderson model should be solved with a many-electron trial wave function. All parameters of the many-electron hamiltonian are taken from LDA+U calculations. The method was applied to NiO and has shown good agreement with experimental photoemission spectra and with the oxygen Kα X-ray emission spectrum.

Electronic structure calculations with dynamical mean-field theory

Abstract: We present a review of the basic ideas and techniques of the spectral density functional theory which are currently used in electronic structure calculations of strongly{correlated materials where the one{electron description breaks down. We illustrate the method with several examples where interactions play a dominant role: systems near metal{insulator transition, systems near volume collapse transition, and systems with local moments.

Orbital Physics in Transition-Metal Oxides

Abstract: An electron in a solid, that is, bound to or nearly localized on the specific atomic site, has three attributes: charge, spin, and orbital. The orbital represents the shape of the electron cloud in solid. In transition-metal oxides with anisotropic-shaped d-orbital electrons, the Coulomb interaction between the electrons (strong electron correlation effect) is of importance for understanding their metal-insulator transitions and properties such as high-temperature superconductivity and colossal magnetoresistance. The orbital degree of freedom occasionally plays an important role in these phenomena, and its correlation and/or order-disorder transition causes a variety of phenomena through strong coupling with charge, spin, and lattice dynamics. An overview is given here on this "orbital physics," which will be a key concept for the science and technology of correlated electrons.

Toward the rational design of non-precious transition metal oxides for oxygen electrocatalysis

Abstract: In this Review, we discuss the state-of-the-art understanding of non-precious transition metal oxides that catalyze the oxygen reduction and evolution reactions. Understanding and mastering the kinetics of oxygen electrocatalysis is instrumental to making use of photosynthesis, advancing solar fuels, fuel cells, electrolyzers, and metal–air batteries. We first present key insights, assumptions and limitations of well-known activity descriptors and reaction mechanisms in the past four decades. The turnover frequency of crystalline oxides as promising catalysts is also put into perspective with amorphous oxides and photosystem II. Particular attention is paid to electronic structure parameters that can potentially govern the adsorbate binding strength and thus provide simple rationales and design principles to predict new catalyst chemistries with enhanced activity. We share new perspective synthesizing mechanism and electronic descriptors developed from both molecular orbital and solid state band structure principles. We conclude with an outlook on the opportunities in future research within this rapidly developing field.

Glassy ferromagnetism and magnetic phase separation in La 1 − x Sr x CoO 3

Abstract: We present the results of a comprehensive investigation of the dc magnetization, ac susceptibility, and magnetotransport properties of the glassy ferromagnet ${\mathrm{La}}_{1\ensuremath{-}x}{\mathrm{Sr}}_{x}{\mathrm{CoO}}_{3}.$ The compositions studied span the range from the end-member ${\mathrm{LaCoO}}_{3}$ $(x=0.0)$ through to $x=0.7.$ These materials have attracted attention recently, primarily due to the spin-state transition phenomena in ${\mathrm{LaCoO}}_{3}$ and the unusual nature of the magnetic ground state for finite x. In this paper we present a consistent picture of the magnetic behavior of ${\mathrm{La}}_{1\ensuremath{-}x}{\mathrm{Sr}}_{x}{\mathrm{CoO}}_{3}$ in terms of short-range ferromagnetic ordering and intrinsic phase separation. At high Sr doping $(xg0.2)$ the system exhibits unconventional ferromagnetism (with a Curie temperature up to 250 K), which is interpreted in terms of the coalescence of short-range-ordered ferromagnetic clusters. Brillouin function fits to the temperature dependence of the magnetization as well as high-temperature Curie-Weiss behavior suggest that the ${\mathrm{Co}}^{3+}$ and ${\mathrm{Co}}^{4+}$ ions are both in the intermediate spin state. At lower Sr doping $(xl0.18)$ the system enters a mixed phase that displays the characteristics of both a spin glass and a ferromagnet. A cusp in the zero-field-cooled dc magnetization, a frequency-dependent peak in the ac susceptibility and time-dependent effects in both dc and ac magnetic properties all point towards glassy behavior. On the other hand, field cooling results in a relatively large ferromagneticlike moment, with zero-field-cooled and field-cooled magnetizations bifurcating at an irreversibility point. Even in the region above $x=0.2$ the out-of-phase component of the ac susceptibility shows frequency-dependent peaks below the Curie temperature (indicative of glassy behavior) which have previously been interpreted in terms of the freezing of clusters. All of the results are consistent with the existence of a strong tendency towards magnetic phase separation in this material, a conclusion which is further reinforced by consideration of the electronic properties. The metal-insulator transition is observed to be coincident with the onset of ferromagnetic ordering $(x=0.18)$ and has a behavior in the doping dependence of the low-temperature conductivity which is strongly suggestive of percolation. This can be interpreted as a percolation transition within the simple ferromagnetic cluster model. On the metallic side of the transition the system exhibits colossal magnetoresistance-type behavior with a peak in the negative magnetoresistance (\ensuremath{\sim}10% in 90 kOe) in the vicinity of the Curie temperature. As the transition is approached from the metallic side we observe the onset of a negative magnetoresistance that increases in magnitude with decreasing temperature, reaching values as large as 90% in a 90-kOe field. This magnetoresistance is enhanced at the metal-insulator transition, where it persists even to room temperature.