Consistent LDA’ + DMFT approach to the electronic structure of transition metal oxides: Charge transfer insulators and correlated metals

We discuss the recently proposed LDA’ + DMFT approach providing a consistent parameter-free treatment of the so-called double counting problem arising within the LDA + DMFT hybrid computational method for realistic strongly correlated materials. In this approach, the local exchange-correlation portion of the electron-electron interaction is excluded from self-consistent LDA calculations for strongly correlated electronic shells, e.g., d-states of transition metal compounds. Then, the corresponding double-counting term in the LDA’ + DMFT Hamiltonian is consistently set in the local Hartree (fully localized limit, FLL) form of the Hubbard model interaction term. We present the results of extensive LDA’ + DMFT calculations of densities of states, spectral densities, and optical conductivity for most typical representatives of two wide classes of strongly correlated systems in the paramagnetic phase: charge transfer insulators (MnO, CoO, and NiO) and strongly correlated metals (SrVO₃ and Sr₂RuO₄). It is shown that for NiO and CoO systems, the LDA’ + DMFT approach qualitatively improves the conventional LDA + DMFT results with the FLL type of double counting, where CoO and NiO were obtained to be metals. Our calculations also include transition-metal 4s-states located near the Fermi level, missed in previous LDA + DMFT studies of these monoxides. General agreement with optical and the X-ray experiments is obtained. For strongly correlated metals, the LDA’ + DMFT results agree well with the earlier LDA + DMFT calculations and existing experiments. However, in general, LDA’ + DMFT results give better quantitative agreement with experimental data for band gap sizes and oxygen-state positions compared to the conventional LDA + DMFT method.     

LDA’+DMFT investigation of electronic structure of K1 − x Fe2 − y Se2 superconductor

We investigate electronic structure of the new iron chalcogenide high temperature superconductor K_1?x Fe_2?y Se₂ (hole doped case with x = 0.24, y = 0.28) in the normal phase using the novel LDA’+DMFT computational approach. We show that this iron chalcogenide is more correlated in a sense of bandwidth renormalization (energy scale compression by factor about 5 in the interval ±1.5 eV), than typical iron pnictides (compression factor about 2), though the Coulomb interaction strength is almost the same in both families. Our results for spectral densities are in general agreement with recent ARPES data on this system. It is found that all Fe-3d(t _2g ) bands crossing the Fermi level have equal renormalization, in contrast to some previous interpretations. Electronic states at the Fermi level are of predominantly xy symmetry. Also we show that LDA’+DMFT results are in better agreement with experimental spectral function maps, than the results of conventional LDA+DMFT. Finally we make predictions for photoemission spectra lineshape for K_0.76Fe_1.72Se₂.     

A full potential all-electron calculation on electronic structure of NiO

We perform a first principle calculation on NiO system, a prototypical correlated electronic system due to partial filled 3d electronic shell, using various density functional theory (DFT) and hybrid functional methods inclusion of spin polarization (SP), on-site Coulomb repulsion U and spin–orbit coupling (SOC) effects. It is shown that localized spin density approximation (LSDA) plus U (LSDA?+?U) correctly reproduce experimental lattice parameter, while spin polarization generalized gradient approximation (SP?+?GGA?+?U) obviously overestimates lattice parameter. LSDA?+?U/SP?+?GGA?+?U band gaps and magnetic moments are in agreement with experimental data, and correctly predict NiO to be an insulator. NiO undergoes a Mott–Hubbard metal–insulator transition (MIT) by addition of Coulomb interaction U. Our LSDA?+?SOC calculation shows that SOC further splitting of Ni d e_g and t_2g orbitals into d_z2, d_xy, d_x2y2 and d_xz?+?d_yz orbitals, and SP nearly cancels out SOC effect, giving rise to symmetry of density of states (DOS) for spin-up and spin-down states, hence appearance of zero net magnetic moment. For LSDA?+?U?+?SOC calculation, combination effect of SP, U and SOC results in non-occupying of spin-up conduction band and a negligible density of states for spin-down states.     

LDA+DMFT study of magnetic transition and metallization in CoO under pressure

The magnetic and spectral properties of the paramagnetic phase of CoO at ambient and high pressures have been calculated within the LDA+DMFT method combining local density approximation (LDA) with dynamical mean-field theory (DMFT). From our results CoO at ambient pressure is a charge transfer insulator in the high-spin t _2g ⁵ e _g ² configuration. The energy gap is continuously decreased, and finally a transition into metallic state occurs with the increase in pressure that is consistent with experimental behavior of electrical resistivity. Notably, the metal-insulator transition in CoO is found to be accompanied by the high-spin to low-spin (HS-LS) transition in agreement with XES data. The metal-insulator transition is orbital selective in the t _2g states of cobalt only, whereas the e _g states become metallic after the spin transition at higher pressures.     

Theoretical electronic transition moments for the Ballik-Ramsay,Fox-Herzberg,and Swan systems OF C2

Potential energy curves and spectroscopic constants T_e, r_e, ω_e, and ω_eχ_e have been calculated for the a³Π_u, b³Σ^-_g, d³Π_g and e³Π_g electronic states of C₂ using self-consistent-field plus configuration-interaction techniques. These results are in excellent agreement with those obtained from experiments. The variation of the electronic transition moment with internuclear separation has been calculated for the Ballik-Ramsay system (b³Σ^-_g-a³Π_u), Fox-Herzberg (e³Π_g-a³Π_u), and Swan (d³Π_g-a³Π_u) band systems. These results are in good agreement with existing experimental and theoretical data.     

On the origin of the shallow and “replica” bands in FeSe monolayer superconductors

We compare the electronic structures of single FeSe layer films on SrTiO₃ substrate (FeSe/STO) and K _x Fe_2-y Se₂ superconductors obtained from extensive LDA and LDA + DMFT calculations with the results of ARPES experiments. It is demonstrated that correlation effects on Fe-3d states are sufficient in principle to explain the formation of the shallow electron-like bands at the M(X)-point. However, in FeSe/STO these effects alone are apparently insufficient for the simultaneous elimination of the hole-like Fermi surface around the Γ-point which is not observed in ARPES experiments. Detailed comparison of ARPES detected and calculated quasiparticle bands shows reasonable agreement between theory and experiment. Analysis of the bands with respect to their origin and orbital composition shows, that for FeSe/STO system the experimentally observed “replica” quasiparticle band at the M-point (usually attributed to forward scattering interactions with optical phonons in SrTiO₃ substrate) can be reasonably understood just as the LDA calculated Fe-3d _xy band, renormalized by electronic correlations. The only manifestation of the substrate reduces to lifting the degeneracy between Fe-3d _xz and Fe-3d _yz bands near M-point. For the case of K _x Fe_2-y Se₂ most bands observed in ARPES can also be understood as correlation renormalized Fe-3d LDA calculated bands, with overall semi-quantitative agreement with LDA + DMFT calculations.     

Temperature dependence of the fundamental absorption edge in CuGaSe2

The temperature dependence of the fundamental absorption edge in CuGaSe₂ single crystals was determined in the temperature range from 15 to 300 K. Above about 120 K the gap energy changes linearly with temperature with dE_g/dT = ? (2.1 ± 0.1) eV K^?1. The downshift in dE_g/dT of the I–III–VI₂ compounds compared to their II–VI analogs is discussed accounting for the p-d hybridization of the uppermost valence band.     

Tailoring the exchange bias of Ni/NiO nanogranular samples by the structure control

The exchange bias (EB) effect has been studied in Ni/NiO nanogranular samples obtained by annealing in H₂, at selected temperatures (200≤T_ann≤300 °C), NiO powder previously milled for 5, 10, 20 and 30 h. Both the as-milled NiO powders and the Ni/NiO samples have been analyzed by X-ray diffraction and the exchange bias properties have been investigated in the 5-200 K temperature range. The structure and the composition of the Ni/NiO samples can be satisfactorily controlled during the synthesis procedure by varying both T_ann and the milling time of the precursor NiO powders. In particular, by increasing this last parameter, the mean grain size of the NiO phase reduces down to the final value of 16 nm and the microstrain increases, which is consistent with an enhancement of the structural disorder. The structure of the milled NiO matrix strongly affects the process of nucleation and growth of the Ni nanocrystallites induced by the H₂ treatments, so that, T_ann being equal, the amount and the mean grain size D_Ni of the Ni phase vary substantially in samples having different milling times. Such features of the Ni phase determine the extent of the Ni/NiO interface and consequently the magnitude of the exchange field H_ex: the highest value (∼940 Oe) has been measured at T=5 K in a sample containing ∼7 wt% Ni and with D_Ni=19 nm. However, in Ni/NiO samples with very different structural characteristics and different values of H_ex at T=5 K, the EB effect vanishes at the same temperature (∼200 K) and the same thermal dependence of H_ex is observed. We consider that the evolution of the EB effect with temperature is ultimately determined by the microstructure of the Ni/NiO interface, which cannot be substantially modified by changing the synthesis parameters, milling time and T_ann.     

The influence of phonons on the optical properties and the conductivity of quasi-one-dimensional metals

The frequency dependent conductivity σ(ω) completely taking into account the interaction between electrons is studied. The shape and the temperature dependence of optical absorption near the frequency of a molecular phonon activated due to the interaction with electrons are found. For a system with attractive sign of the e-e backward scattering amplitude g₁<0 an absorption edge near the gap 2Δ in the electronic spectrum is studied. A low frequency conductivity is discussed. The properties under consideration depend essentially on the magnitudes of e-e interactions and are critical to the sign of g₁.     

Spectral and luminescent study of reduced forms of Pd-octaethylporphin

It is shown by electron absorption spectroscopy methods that the reduction of Pd-octaethylporphin does not touch the unfilled d _x ²-_y ² orbitals of metal. In the reduction products (mono-and dianions), excess electrons are distributed on the lowest vacant molecular e _g (π*) orbital of the ligand. This does not contradict the results of the quantum-chemical calculation of electronic states of neutral Pd-porphyrins by the extended Hückel method that are presented in the literature. Differences in electronic absorption spectra of π-anions of Pd and Zn complexes are attributed to the distortion of the plane geometry of the tetrapyrrole skeleton due to the displacement of the Pd(II) ion from the macrocycle plane. Mono-and dianions of their Pd complex lose the ability to be luminescent. The emissive capacity is reconstructed in the product of π-dianion protonation, which is called phlorin-anion (π-monoanion of Pd-octaethylporphin phlorin). As the temperature is decreased from room temperature to 77 K, the fluorescence spectrum of this product becomes narrower, its peak shifts to the blue region, and the quantum yield of luminescence increases. Specific features of the spectral properties of phlorin-anion are described by conformational changes in the excited state. Phlorin-anion was found to quench luminescence of neutral Pd-octaethylporphin molecules at room temperature.     

Electronic Structure of FeSe Monolayer Superconductors: Shallow Bands and Correlations

Electronic spectra of typical single FeSe layer superconductor—FeSe monolayer film on SrTiO₃ substrate (FeSe/STO) obtained from ARPES data reveal several puzzles: what is the origin of shallow and the so called “replica” bands near the M-point and why the hole-like Fermi surfaces near the Γ-point are absent. Our extensive LDA+DMFT calculations show that correlation effects on Fe-3d states can almost quantitatively reproduce rather complicated band structure, which is observed in ARPES, in close vicinity of the Fermi level for FeSe/STO. Rather unusual shallow electron-like bands around the M-point in the Brillouin zone are well reproduced. Detailed analysis of the theoretical and experimental quasiparticle bands with respect to their origin and orbital composition is performed. It is shown that for FeSe/STO system the LDA calculated Fe-3d _xy band, renormalized by electronic correlations within DMFT gives the quasiparticle band almost exactly in the energy region of the experimentally observed “replica” quasiparticle band at the Mpoint. However, correlation effects alone are apparently insufficient to eliminate the hole-like Fermi surfaces around the Γ-point, which are not observed in most ARPES experiments. The Fermi surfaces remain here even if Coulomb and/or Hund interaction strengths are increased while overall agreement with ARPES worsens. Increase of number of electrons also does not lead to vanishing of this Fermi surface and makes agreement of LDA+DMFT results with ARPES data much worse. We also present some simple estimates of “forward scattering” electron-optical phonon interaction at FeSe/STO interface, showing that it is apparently irrelevant for the formation of “replica” band in this system and significant increase of superconducting T _c .     

Elimination of the mott interband s-d enhancement of the electrical resistance of nickel and platinum owing to the excitation of electrons by femtosecond laser pulses

The dependence of electrical, σ, and thermal, κ, conductivities of metals on the electron temperature T _e at high (～1 eV) T _e values has been calculated. The two-temperature states for which the temperature T _e of heated electrons exceeds the temperature T _i of ions in the crystal lattice result from the excitation of electrons by femtosecond laser pulses. It is well known that the existence of empty d levels with a high density of states near the Fermi surface (as, e.g., in nickel, platinum, and iron) leads to a pronounced enhancement of the electrical resistance (Mott, 1936). This is due to an increase in the statistical factor related to the electron transitions to the empty states induced by collisions with phonons. It is found that the excitation of the electron subsystem significantly reduces the electron-phonon scattering to unoccupied d states since the chemical potential μ(T _e ) rises above the upper edge of the d band. The decrease in the scattering probability leads to the anomalous behavior of the conductivity σ_el-ph, which increases with the temperature T _e . Such a behavior turns out to be inverse with respect to the usual situation in condensed matter.     

Kondo anomalies of heat conductivity and Lorenz ratio in normal state (La,Ce) Al2

The thermal conductivity of LaAl₂ and of two dilute (La, Ce)Al₂ alloys was measured in the normal state between 0.4 and 8 K. From the lattice conductivity of LaAl₂ a high dislocation densityN _d caused by the arc melting process can be inferred. After annealingN _d is reduced by an order of magnitude. For the (La, Ce)Al₂ samples minima are observed at 5 K in theW ^e ·T vs.T curves (W ^e =electronic thermal resistivity). Below 1 K the quantityW ^e ·T is linear in (— lnT). The electronic Lorenz ratioL ^e (T)=ρ(T)/W ^e (T) ·T shows a maximum at 2 K with a value 23% aboveL ^e (0). It is for the first time that this Kondo anomaly is established in its full temperature dependence.     

Theoretical investigation of the molecular structure and transition dipole moments of the NaK low lying electronic states

The electronic structure and the spectroscopic constants of the low lying electronic states of the NaK⁺ ionic molecule have been determined through using an ab initio approach involving a non-empirical pseudopotential for the Na and K cores and core valence correlation correction. The potential energy of nearly 26 electronic states of ²Σ⁺, ²Π, and ²Δ symmetries has been calculated up to their dissociation limit Na(4d) + K⁺ and Na⁺ + K(6s). Their spectroscopic constants (R_e, D_e, T_e, ω_e, ω_eχ_e, and B_e) are derived and compared with the few available theoretical studies. A good agreement has been found for the ground state and few excited states with previous works. New potential energy curves were presented, for the first time, for the higher excited states. Numerous avoided crossing between electronic states of ²Σ⁺, ²Π symmetries have been localized and analyzed. Their existences are related to the charge transfer between the two ionic molecules Na⁺K and NaK⁺. Furthermore, we have determined the transition dipole moments for several states and analyzed the avoided crossings related to charge transfer between alkaline atoms.     

Magnetic properties of Li<Subscript>2</Subscript>RuO<Subscript>3</Subscript> as studied by NMR and LDA + DMFT calculations

We present results of the combined study of the magnetic properties of Li₂RuO₃ by means of nuclear magnetic resonance (NMR) spectroscopy and theoretical dynamical mean-field theory (LDA + DMFT) calculations. The NMR data clearly show the onset of a thermal activation process in the high temperature region, T > 560K, which is tentatively ascribed to the formation of the valence bond liquid. The LDA + DMFT calculations demonstrate that the magnetic response at these temperatures is mostly due to the xz/yz orbitals, while the xy orbitals of Ru still form molecular orbitals. Thus, Ru ions are in the orbital-selective state in the high temperature phase of Li₂RuO₃.     

Magnetic susceptibility and superconductivity of cubic vanadium nitrides

The superconducting transition temperature T_C and the magnetic susceptibility from 77 to 300°K have been measured on five cubic vanadium nitrides: VN, VN_0.91, VN_0.82, VN_0.84 and VN_0.75. The materials were carefully prepared to exclude oxygen and ferromagnetic impurities.The value of T_C, falls from 8.1°K for VN to 2.3°K for VN_0.75. The mass-susceptibility decreases from +3.94 × 10^?6e.m.u./g for VN to 1.88 × 10^?6e.m.u./g for VN_0.75 at 300°K. All samples showed a small positive slope for the susceptibility temperature curve.The results are discussed in terms of the rigid band model. The main features are a high density of states of d electrons, 2.4 states/atom eV for VN that drops off as the nitrogen content decreases, to 0.8 states/atom eV.Preliminary considerations indicate that many-body effects could reduce this density of states by as much as a factor of 2. Lack of experimental results on Knight shifts and low-temperature specific heats prevent a more quantitative estimate being made.     

Temperature shift of the CdxHg1−xTe energy gap

The temperature coefficient of the Cd_xHg_1?xTe energy gap dE_g/dT as a sum of lattice dilatation and the phonon-electron interaction terms has been calculated as the function of molar composition x, for 0?x?0.3, in the temperature range 4.2–300 K. A non-linear dependence of $\text{d}\text{E}{}_{\mathrm{g}}\text{d}\text{T}$ vs x and a strong effect of temperature on $\text{d}\text{E}{}_{\mathrm{g}}\text{d}\text{T}$ values have been obtained and a comparison with experimental data is discussed.     

On the interpretation of valence band photoemission spectra of NiO

The valence band photoemission spectrum and the L₃VV Auger spectrum of NiO are compared. The satellite found in the valence band of NiO and other Ni compounds is interpreted as an unscreened 3d⁷ final state, whereas the main d-emission is a 3d⁷ final state screened by a d electron in an exitonic state.     

Comparative study of electronic structure of new superconductors (Sr, Ca)Pd2As2 and related compound BaPd2As2

This paper presents the comparative study of LDA calculated electronic structure of new isostructural to iron based systems superconductors (Sr, Ca)Pd₂As₂ with T _c about 1 K and similar but structurally different system BaPd₂As₂. Despite chemical formula looks similar to iron superconductors and even main structural motif is the same—layers of Fe square lattices, electronic structure of (Sr, Ca)Pd₂As₂ and BaPd₂As₂ differs from Fe (As, Se)-HTSC completely. All these systems have essentially three dimensional Fermi surfaces in contrast to Fe (As, Se) materials. The Fermi level is crossed by low intensive tails of Pd-4d and As-4p states. However, (Sr, Ca)Pd₂As₂ and BaPd₂As₂ materials have rather well developed peaks of Pd-4d (x ² ? y ²) band. Thus, by doping of about 2 holes per unit cell one can increase density of states at the Fermi level by a factor about 2.5. Since experimentally these compounds were found to be simple BCS superconductors the hole doping may considerably increase T _c . LDA calculated total densities of states at the Fermi level for stoichiometric systems perfectly agree with experimental estimates signifying rather small role of electronic correlations.     

Photoconductivity spectra of HgCr2Se4

The photoconductivity spectra of ferromagnetic semiconductor HgCr₂Se₄ single crystals in the intrinsic transition region were measured at a number of fixed temperatures covering T_c = 106 K. The photoconductivity edge, 0.88 eV, at room temperature shifted to 0.35 eV at 52 K.The temperature dependence of the photoconductivity edge is in good correspondence with that of the absorption edge, and is explained qualitatively well with the calculated spin correlation functions in spinels.From the theoretical calculations by Kambara et al., the lowest transition associated with the photoconduction in HgCr₂Se₄ was interpreted to be the electronic transition from the highest d? to the lowest A [dγ-p] states for up-spin at X point. The many doby effects should be taken into account.