Global Phase Diagram of a Spin-Orbital Kondo Impurity Model and the Suppression of Fermi-Liquid Scale.

Many correlated metallic materials are described by Landau Fermi-liquid theory at low energies, but for Hund metals the Fermi-liquid coherence scale T_{FL} is found to be surprisingly small. In this Letter, we study the simplest impurity model relevant for Hund metals, the three-channel spin-orbital Kondo model, using the numerical renormalization group (NRG) method and compute its global phase diagram. In this framework, T_{FL} becomes arbitrarily small close to two new quantum critical points that we identify by tuning the spin or spin-orbital Kondo couplings into the ferromagnetic regimes. We find quantum phase transitions to a singular Fermi-liquid or a novel non-Fermi-liquid phase. The new non-Fermi-liquid phase shows frustrated behavior involving alternating overscreenings in spin and orbital sectors, with universal power laws in the spin (ω^{-1/5}), orbital (ω^{1/5}) and spin-orbital (ω^{1}) dynamical susceptibilities. These power laws, and the NRG eigenlevel spectra, can be fully understood using conformal field theory arguments, which also clarify the nature of the non-Fermi-liquid phase.

Low-Temperature Thermopower in CoSbS.

We report on giant thermopower of S=2.5 mV/K in CoSbS single crystals: a material that shows strong high-temperature thermoelectric performance when doped with Ni or Se. Changes of low-temperature thermopower induced by a magnetic field point to the mechanism of electronic diffusion of carriers in the heavy valence band. Intrinsic magnetic susceptibility is consistent with the Kondo-insulatorlike accumulation of electronic states around the gap edges. This suggests that giant thermopower stems from temperature-dependent renormalization of the noninteracting bands and buildup of the electronic correlations on cooling.

Direct Detection of Dimer Orbitals in Ba_{5}AlIr_{2}O_{11}.

The electronic states of many Mott insulators, including iridates, are often conceptualized in terms of localized atomic states such as the famous "J_{eff}=1/2 state." Although orbital hybridization can strongly modify such states and dramatically change the electronic properties of materials, probing this process is highly challenging. In this Letter, we directly detect and quantify the formation of dimer orbitals in an iridate material Ba_{5}AlIr_{2}O_{11} using resonant inelastic x-ray scattering. Sharp peaks corresponding to the excitations of dimer orbitals are observed and analyzed by a combination of density functional theory calculations and theoretical simulations based on an Ir-Ir cluster model. Such partially delocalized dimer states lead to a redefinition of the angular momentum of the electrons and changes in the magnetic and electronic behaviors of the material. We use this to explain the reduction of the observed magnetic moment with respect to predictions based on atomic states. This study opens new directions to study dimerization in a large family of materials, including solids, heterostructures, molecules, and transient states.

Unveiling the Superconducting Mechanism of Ba_{0.51}K_{0.49}BiO_{3}.

The mechanism of high superconducting transition temperatures (T_{c}) in bismuthates remains under debate despite more than 30 years of extensive research. Our angle-resolved photoemission spectroscopy studies on Ba_{0.51}K_{0.49}BiO_{3} reveal an unexpectedly 34% larger bandwidth than in conventional density functional theory calculations. This can be reproduced by calculations that fully account for long-range Coulomb interactions-the first direct demonstration of bandwidth expansion due to the Fock exchange term, a long-accepted and yet uncorroborated fundamental effect in many body physics.Furthermore, we observe an isotropic superconducting gap with 2Δ_{0}/k_{B}T_{c}=3.51±0.05, and strong electron-phonon interactions with a coupling constant λ∼1.3±0.2. These findings solve a long-standing mystery-Ba_{0.51}K_{0.49}BiO_{3} is an extraordinary Bardeen-Cooper-Schrieffer superconductor, where long-range Coulomb interactions expand the bandwidth, enhance electron-phonon coupling, and generate the high T_{c}. Such effects will also be critical for finding new superconductors.

Correlation-Enhanced Odd-Parity Interorbital Singlet Pairing in the Iron-Pnictide Superconductor LiFeAs.

The rich variety of iron-based superconductors and their complex electronic structure lead to a wide range of possibilities for gap symmetry and pairing components. Here we solve in the two-Fe Brillouin zone the full frequency-dependent linearized Eliashberg equations to investigate spin-fluctuations mediated Cooper pairing for LiFeAs. The magnetic excitations are calculated with the random phase approximation on a correlated electronic structure obtained with density functional theory and dynamical mean field theory. The interaction between electrons through Hund's coupling promotes both the intraorbital d_{xz(yz)} and the interorbital magnetic susceptibility. As a consequence, the leading pairing channel, conventional s^{+-}, acquires sizable interorbital d_{xy}-d_{xz(yz)} singlet pairing with odd parity under glide-plane symmetry. The combination of intra- and interorbital components makes the results consistent with available experiments on the angular dependence of the gaps observed on the different Fermi surfaces.

Metal-Insulator Transition in VO_{2}: A DFT+DMFT Perspective.

We present a theoretical investigation of the electronic structure of rutile (metallic) and M_{1} and M_{2} monoclinic (insulating) phases of VO_{2} employing a fully self-consistent combination of density functional theory and embedded dynamical mean field theory calculations. We describe the electronic structure of the metallic and both insulating phases of VO_{2}, and propose a distinct mechanism for the gap opening. We show that Mott physics plays an essential role in all phases of VO_{2}: undimerized vanadium atoms undergo classical Mott transition through local moment formation (in the M_{2} phase), while strong superexchange within V dimers adds significant dynamic intersite correlations, which remove the singularity of self-energy for dimerized V atoms. The resulting transition from rutile to dimerized M_{1} phase is adiabatically connected to the Peierls-like transition, but is better characterized as the Mott transition in the presence of strong intersite exchange. As a consequence of Mott physics, the gap in the dimerized M_{1} phase is temperature dependent. The sole increase of electronic temperature collapses the gap, reminiscent of recent experiments.

Dynamical Mean-Field Theory Plus Numerical Renormalization-Group Study of Spin-Orbital Separation in a Three-Band Hund Metal.

We show that the numerical renormalization group is a viable multi-band impurity solver for dynamical mean-field theory (DMFT), offering unprecedented real-frequency spectral resolution at arbitrarily low energies and temperatures. We use it to obtain a numerically exact DMFT solution to the Hund metal problem for a three-band model on a Bethe lattice at 1/3 filling. The ground state is a Fermi liquid. The one-particle spectral function undergoes a coherence-incoherence crossover with increasing temperature, with spectral weight being transferred from low to high energies. Further, it exhibits a strong particle-hole asymmetry. In the incoherent regime, the self-energy displays approximate power-law behavior for positive frequencies only. The spin and orbital spectral functions show "spin-orbital separation": spin screening occurs at much lower energies than orbital screening. The renormalization group flows clearly reveal the relevant physics at all energy scales.

From antiferromagnetic insulator to correlated metal in pressurized and doped LaMnPO.

Widespread adoption of superconducting technologies awaits the discovery of new materials with enhanced properties, especially higher superconducting transition temperatures T(c). The unexpected discovery of high T(c) superconductivity in cuprates suggests that the highest T(c)s occur when pressure or doping transform the localized and moment-bearing electrons in antiferromagnetic insulators into itinerant carriers in a metal, where magnetism is preserved in the form of strong correlations. The absence of this transition in Fe-based superconductors may limit their T(c)s, but even larger T(c)s may be possible in their isostructural Mn analogs, which are antiferromagnetic insulators like the cuprates. It is generally believed that prohibitively large pressures would be required to suppress the effects of the strong Hund's rule coupling in these Mn-based compounds, collapsing the insulating gap and enabling superconductivity. Indeed, no Mn-based compounds are known to be superconductors. The electronic structure calculations and X-ray diffraction measurements presented here challenge these long held beliefs, finding that only modest pressures are required to transform LaMnPO, isostructural to superconducting host LaFeAsO, from an antiferromagnetic insulator to a metallic antiferromagnet, where the Mn moment vanishes in a second pressure-driven transition. Proximity to these charge and moment delocalization transitions in LaMnPO results in a highly correlated metallic state, the familiar breeding ground of superconductivity.

Evidence of strong correlations and coherence-incoherence crossover in the iron pnictide superconductor KFe2As2.

Using resistivity, heat-capacity, thermal-expansion, and susceptibility measurements we study the normal-state behavior of KFe2As2. Both the Sommerfeld coefficient (γ≈103 mJ mol(-1) K(-2)) and the Pauli susceptibility (χ≈4×10(-4)) are strongly enhanced, which confirm the existence of heavy quasiparticles inferred from previous de Haas-van Alphen and angle-resolved photoemission spectroscopy experiments. We discuss this large enhancement using a Gutzwiller slave-boson mean-field calculation, which shows the proximity of KFe2As2 to an orbital-selective Mott transition. The temperature dependence of the magnetic susceptibility and the thermal expansion provide strong experimental evidence for the existence of a coherence-incoherence crossover, similar to what is found in heavy fermion and ruthenate compounds, due to Hund's coupling between orbitals.

Fluctuating valence in a correlated solid and the anomalous properties of delta-plutonium.

Although the nuclear properties of the late actinides (plutonium, americium and curium) are fully understood and widely applied to energy generation, their solid-state properties do not fit within standard models and are the subject of active research. Plutonium displays phases with enormous volume differences, and both its Pauli-like magnetic susceptibility and resistivity are an order of magnitude larger than those of simple metals. Curium is also highly resistive, but its susceptibility is Curie-like at high temperatures and orders antiferromagnetically at low temperatures. The anomalous properties of the late actinides stem from the competition between itinerancy and localization of their f-shell electrons, which makes these elements strongly correlated materials. A central problem in this field is to understand the mechanism by which these conflicting tendencies are resolved in such materials. Here we identify the electronic mechanisms responsible for the anomalous behaviour of late actinides, revisiting the concept of valence using a theoretical approach that treats magnetism, Kondo screening, atomic multiplet effects and crystal field splitting on the same footing. We find that the ground state in plutonium is a quantum superposition of two distinct atomic valences, whereas curium settles into a magnetically ordered single valence state at low temperatures. The f(7) configuration of curium is contrasted with the multiple valences of the plutonium ground state, which we characterize by a valence histogram. The balance between the Kondo screening and magnetism is controlled by the competition between spin-orbit coupling, the strength of atomic multiplets and the degree of itinerancy. Our approach highlights the electronic origin of the bonding anomalies in plutonium, and can be applied to predict generalized valences and the presence or absence of magnetism in other compounds starting from first principles.

Kinetic frustration and the nature of the magnetic and paramagnetic states in iron pnictides and iron chalcogenides.

The iron pnictide and chalcogenide compounds are a subject of intensive investigations owing to their surprisingly high temperature superconductivity. They all share the same basic building blocks, but there is significant variation in their physical properties, such as magnetic ordered moments, effective masses, superconducting gaps and transition temperature (T(c)). Many theoretical techniques have been applied to individual compounds but no consistent description of the microscopic origin of these variations is available. Here we carry out a comparative theoretical study of a large number of iron-based compounds in both their magnetic and paramagnetic states. Taking into account correlation effects and realistic band structures, we describe well the trends in all of the physical properties such as the ordered moments, effective masses and Fermi surfaces across all families of iron compounds, and find them to be in good agreement with experiments. We trace variation in physical properties to variations in the key structural parameters, rather than changes in the screening of the Coulomb interactions. Our results also provide a natural explanation of the strongly Fermi-surface-dependent superconducting gaps observed in experiments.

Many-body effects in iron pnictides and chalcogenides: nonlocal versus dynamic origin of effective masses.

We apply the quasiparticle self-consistent GW approximation (QSGW) to some of the iron pnictide and chalcogenide superconductors. We compute Fermi surfaces and density of states, and find excellent agreement with experiment, substantially improving over standard band-structure methods. Analyzing the QSGW self-energy we discuss nonlocal and dynamic contributions to effective masses. We present evidence that the two contributions are mostly separable, since the quasiparticle weight is found to be essentially independent of momentum. The main effect of nonlocality is captured by the static but nonlocal QSGW effective potential. Moreover, these nonlocal self-energy corrections, absent in, e.g., dynamical mean field theory, can be relatively large. We show, on the other hand, that QSGW only partially accounts for dynamic renormalizations at low energies. These findings suggest that QSGW combined with dynamical mean field theory will capture most of the many-body physics in the iron pnictides and chalcogenides.

Model of the electron-phonon interaction and optical conductivity of Ba(1-x)K(x)BiO(3) superconductors.

We investigate the physical properties of the Ba(1-x)K(x)BiO(3) compounds with a focus on the optical properties. Results from the simple Holstein model, describing a single band coupled to an oxygen breathing mode with parameters derived from first principles calculations, are in excellent agreement with a broad range of experimental information. It accounts for an insulating parent compound at x=0, with a direct (optical) and an indirect gap, and a metal insulator transition around x=0.38. Strong electron-phonon coupling leads to spectral weight redistribution over a frequency scale much larger than the characteristic phonon frequency and to strongly anharmonic phonons. We find that the metallic phase in the vicinity of phase boundary is close to the polaronic regime.

Temperature-dependent Fermi surface evolution in heavy fermion CeIrIn5.

We address theoretically the evolution of the heavy fermion Fermi surface (FS) as a function of temperature (T), using a first principles dynamical mean-field theory approach combined with density functional theory. We focus on the archetypical heavy electrons in CeIrIn{5}. Upon cooling, both the quantum oscillation frequencies and cyclotron masses show logarithmic scaling behavior [∼ln(T{0}/T)] with different characteristic temperatures T{0}=130 and 50 K, respectively. The enlargement of the electron FSs at low T is accompanied by topological changes around T=10-50 K. The resistivity coherence peak observed at T≃50 K is the result of the competition between the binding of incoherent 4f electrons to the spd conduction electrons at Fermi level (E{F}) and the formation of coherent 4f electrons.

Electronic correlations and unconventional spectral weight transfer in the high-temperature pnictide BaFe(2-x)Co(x)As(2) superconductor using infrared spectroscopy.

We report an infrared optical study of the pnictide high-temperature superconductor BaFe(1.84)Co(0.16)As(2) and its parent compound BaFe(2)As(2). We demonstrate that electronic correlations are moderately strong and do not change across the spin-density wave transition or with doping. By examining the energy scale and direction of spectral weight transfer, we argue that Hund's coupling J is the primary mechanism that gives rise to correlations.

Unusual electronic and vibrational properties in the colossal thermopower material FeSb2.

The iron antimonide FeSb2 possesses an extraordinarily high thermoelectric power factor at low temperature, making it a leading candidate for cryogenic thermoelectric cooling devices. However, the origin of this unusual behavior is controversial, having been variously attributed to electronic correlations as well as the phonon-drag effect. The optical properties of a material provide information on both the electronic and vibrational properties. The optical conductivity reveals an anisotropic response at room temperature; the low-frequency optical conductivity decreases rapidly with temperature, signalling a metal-insulator transition. One-dimensional semiconducting behavior is observed along the b axis at low temperature, in agreement with first-principle calculations. The infrared-active lattice vibrations are also symmetric and extremely narrow, indicating long phonon relaxation times and a lack of electron-phonon coupling. Surprisingly, there are more lattice modes along the a axis than are predicted from group theory; several of these modes undergo significant changes below about 100 K, hinting at a weak structural distortion or phase transition. While the extremely narrow phonon line shapes favor the phonon-drag effect, the one-dimensional behavior of this system at low temperature may also contribute to the extraordinarily high thermopower observed in this material.

Self-energy behavior away from the Fermi surface in doped Mott insulators.

We analyze self-energies of electrons away from the Fermi surface in doped Mott insulators using the dynamical cluster approximation to the Hubbard model. For large onsite repulsion, U, and hole doping, the magnitude of the self-energy for imaginary frequencies at the top of the band ([Formula: see text]) is enhanced with respect to the self-energy magnitude at the bottom of the band ([Formula: see text]). The self-energy behavior at these two [Formula: see text]-points is switched for electron doping. Although the hybridization is much larger for (0, 0) than for [Formula: see text], we demonstrate that this is not the origin of this difference. Isolated clusters under a downward shift of the chemical potential, [Formula: see text], at half-filling reproduce the overall self-energy behavior at (0, 0) and [Formula: see text] found in low hole doped embedded clusters. This happens although there is no change in the electronic structure of the isolated clusters. Our analysis shows that a downward shift of the chemical potential which weakly hole dopes the Mott insulator can lead to a large enhancement of the [Formula: see text] self-energy for imaginary frequencies which is not associated with electronic correlation effects, even in embedded clusters. Interpretations of the strength of electronic correlations based on self-energies for imaginary frequencies are, in general, misleading for states away from the Fermi surface.

Dynamical correlations in multiorbital Hubbard models: fluctuation exchange approximations.

We study the two-band degenerate Hubbard model using the fluctuation exchange approximation (FLEX) and compare the results with quantum Monte Carlo (QMC) calculations. Both the self-consistent and the non-self-consistent versions of the FLEX scheme are investigated. We find that, unlike in the one-band case, in the multiband case, good agreement with the quantum Monte Carlo results is obtained within the electron-electron T-matrix approximation using the full renormalization of the one-particle propagators. The crossover to strong coupling and the formation of satellites is more clearly visible in the non-self-consistent scheme. Finally we discuss the behaviour of the FLEX for higher orbital degeneracy.

Protected Fe valence in quasi-two-dimensional α-FeSi2.

We report the first comprehensive study of the high temperature form (α-phase) of iron disilicide. Measurements of the magnetic susceptibility, magnetization, heat capacity and resistivity were performed on well characterized single crystals. With a nominal iron d(6) configuration and a quasi-two-dimensional crystal structure that strongly resembles that of LiFeAs, α-FeSi2 is a potential candidate for unconventional superconductivity. Akin to LiFeAs, α-FeSi2 does not develop any magnetic order and we confirm its metallic state down to the lowest temperatures (T = 1.8 K). However, our experiments reveal that paramagnetism and electronic correlation effects in α-FeSi2 are considerably weaker than in the pnictides. Band theory calculations yield small Sommerfeld coefficients of the electronic specific heat γ = Ce/T that are in excellent agreement with experiment. Additionally, realistic many-body calculations further corroborate that quasi-particle mass enhancements are only modest in α-FeSi2. Remarkably, we find that the natural tendency to vacancy formation in the iron sublattice has little influence on the iron valence and the density of states at the Fermi level. Moreover, Mn doping does not significantly change the electronic state of the Fe ion. This suggests that the iron valence is protected against hole doping and indeed the substitution of Co for Fe causes a rigid-band like response of the electronic properties. As a key difference from the pnictides, we identify the smaller inter-iron layer spacing, which causes the active orbitals near the Fermi level to be of a different symmetry in α-FeSi2. This change in orbital character might be responsible for the lack of superconductivity in this system, providing constraints on pairing theories in the iron based pnictides and chalcogenides.

Ground state theory of delta-Pu

Correlation effects are important for making predictions in the delta phase of Pu. Using a realistic treatment of the intra-atomic Coulomb correlations we address the long-standing problem of computing ground state properties. The equilibrium volume is obtained in good agreement with experiment when taking into account Hubbard U of the order 4 eV. For this U, the calculation predicts a 5f(5) atomiclike configuration with L = 5, S = 5/2, and J = 5/2 and shows a nearly complete compensation between spin and orbital magnetic moments.