A fully ab initio scheme based on quantum chemical wavefunction methods is used to investigate the correlated multiorbital electronic structure of a 3d-metal compound, LaCoO3. The strong short-range electron correlations, involving both Co and O orbitals, are treated by multireference techniques. The use of effective parameters like the Hubbard U and interorbital U', J terms and the problems associated with their explicit calculation are avoided with this approach. We provide new insight into the spin-state transition at about 90 K and the nature of charge carriers in the doped material. Our results indicate the formation of a t4e2 high-spin state in LaCoO3 for T>90 K. Additionally, we explain the paramagnetic phase in the low-temperature lightly doped compound through the formation of Zhang-Rice-like O hole states and ferromagnetic clusters.
Recently, strong reduction of the quasiparticle peaks and pronounced incoherent structures have been observed in the photoemission spectra of layered cobaltates. Surprisingly, these many-body effects are found to increase near the band insulator regime. We explain these unexpected observations in terms of a novel spin-polaron model for CoO_2 planes which is based on a fact of the spin-state quasidegeneracy of Co^{3+} ions in oxides. Scattering of the photoholes on spin-state fluctuations suppresses their coherent motion. The observed ``peak-dip-hump'' type lineshapes are well reproduced by the…
We present a numerical treatment of a spin-orbital polaron model for Na_xCoO_2 at small hole concentration (0.7 < x < 1). We demonstrate how the polarons account for the peculiar magnetic properties of this layered compound: They explain the large susceptibility; their internal degrees of freedom lead both to a negative Curie-Weiss temperature and yet to a ferromagnetic intra-layer interaction, thereby resolving a puzzling contradiction between these observations. We make specific predictions on the momentum and energy location of excitations resulting from the internal degrees of freedom of t…
We have studied the sub-picosecond quasiparticle dynamics in the perovskite manganite La0.7Ca0.3MnO3 and the layered manganite La1.4Sr1.6Mn2O7 using ultrafast optical spectroscopy. We found that for T > TC, initial relaxation proceeds on the time scale of several hundred femtoseconds and corresponds to the redressing of a photoexcited electron to its polaronic ground state. The temperature and dimensionality dependence of this polaron redressing time provides insight into the relationship between polaronic motion and spin dynamics on a sub-picosecond time scale. We also observe a crossover to …
Transition metal oxides are promising candidates for thermoelectric applications, because they are stable at high temperature and because strong electronic correlations can generate large Seebeck coefficients, but their thermoelectric power factors are limited by the low electrical conductivity. We report transport measurements on Ca3Co4O9 films on various perovskite substrates and show that reversible incorporation of oxygen into SrTiO3 and LaAlO3 substrates activates a parallel conduction channel for p-type carriers, greatly enhancing the thermoelectric performance of the film-substrate syst…
The magnetic properties of polycrystaline La0.5Ba0.5CoO2.5+d (d = 0.44 and 0.485) where investigated using muon spin relaxation and bulk magnetization experiments. Below a Curie temperature of T_C = 160 K and 180 K, respectively, a magnetic phase with a macroscopic ferromagnetic moment forms. muSR proves that the full volume inhomogeneously orders at T_C but that there is microscopically a phase separation into phase volumes possessing a fully static and a slow magnetic dynamic behavior. A peak in the dynamic relaxation rate 35 K respectively 55 K below the Curie temperature indicates the free…
Polaron-driven switching of octupolar order in doped 5d$^2$ double perovskite
University of Vienna（维也纳大学）；CPHT, CNRS, École polytechnique, Institut Polytechnique de Paris（巴黎综合理工学院）；Collège de France, Université PSL（法兰西公学院）；Department of Physics and Astronomy ”Augusto Righi”, Alma Mater Studiorum - Università di Bologna（博洛尼亚大学）
We present first principles LDA+U calculations of electronic structure and magnetic state for LaCoO3 and HoCoO3. Low Spin to Intermediate Spin state transition was found in our calculations using experimental crystallographic data for both materials with a much higher transition temperature for HoCoO3, which agrees well with the experimental estimations. Low Spin state t6e0 (non-magnetic) to Intermediate Spin state t5e1 (magnetic) transition of Co(3+) ions happens due to the competition between crystal field t_2g-e_g splitting and effective exchange interaction between 3$d$ spin-orbitals. We s…
We report x-ray scattering studies of broad peaks located at a (0.5 0 0)/(0 0.5 0)-type wavevector in the paramagnetic insulating phases of La_{0.7}Ca_{0.3}MnO_{3} and Pr_{0.7}Ca_{0.3}MnO_{3}. We interpret the scattering in terms of correlated polarons and measure isotropic correlation lengths of 1-2 lattice constants in both samples. Based on the wavevector and correlation lengths, the correlated polarons are found to be consistent with CE-type bipolarons. Differences in behavior between the samples arise as they are cooled through their respective transition temperatures and become ferromagn…
We investigate the doping dependence of the nanoscale electronic and magnetic inhomogeneities in the hole-doping range 0.002<x<0.1 of cobalt based perovskites, La{1-x}Sr_xCoO_3. Using single crystal inelastic neutron scattering and magnetization measurements we show that the lightly doped system exhibits magneto-electronic phase separation in form of spin-state polarons. Higher hole doping leads to a decay of spin-state polarons in favor of larger-scale magnetic clusters, due to competing ferromagnetic correlations of Co^{3+} ions which are formed by neighboring polarons. The present data give…
We use the Momentum Average approximation together with perturbative approaches, in the appropriate limits, to study the single polaron physics on a perovskite lattice inspired by BaBiO3. We investigate electron-phonon coupling of the Peierls type whereby the motion of ions modulates the values of the hopping integrals between sites, and show that it cannot be mapped onto the simpler one-band Holstein model in the whole parameter space. This is because the dispersion of the Peierls polaron has sharp transitions where the ground-state momentum jumps between high-symmetry points in the Brillouin…
Temperature dependent optical conductivity spectra of a La0.7Ca0.3MnO3 (LCMO) sample were measured. In the metallic regime at very low temperatures, they clearly showed two types of absorption features, i.e., a sharp Drude peak and a broad mid-infrared absorption band, which could be explained as coherent and incoherent bands of a large lattice polaron. This elementary excitation in LCMO was found to be in a strong coupling regime and to have interactions with the spin degree of freedom.
Single crystals of electron-doped SrMnO3 with a cubic perovskite structure have been systematically investigated as the most canonical (orbital-degenerate) double-exchange system, whose ground states have been still theoretically controversial. With only 1-2% electron doping by Ce substitution for Sr, a G-type antiferromagnetic metal with a tiny spin canting in a cubic lattice shows up as the ground state, where the Jahn-Teller polarons with heavy mass are likely to form. Further electron doping above 4%, however, replaces this isotropic metal with an insulator with tetragonal lattice distorti…
We systematically studied the magnetic and transport properties for the polycrystalline samples of Fe-doped perovskite cobaltites: Pr$_{1-y}$Ca$_{y}$Co$_{1-x}$Fe$_x$O$_3$ ($y$=0.3, $x$=0-0.15; $y$=0.45, $x$=0-0.3) and Gd$_{0.55}$Sr$_{0.45}$Co$_{1-x}$Fe$_x$O$_{3}$ ($x$=0-0.3). Fe doping leads to an enhancement of the ferromagnetism in the systems of Pr$_{1-y}$Ca$_{y}$Co$_{1-x}$Fe$_x$O$_3$, while the ferromagnetism is suppressed with further increasing Fe content and spin-glass behavior is observed at high doping level of Fe. In contrast, the ferromagnetism is suppressed in the system Gd$_{0.55}…
We have studied the magnetic properties and spin-dynamics of the structurally-ordered double perovskite Sr$_2$CoOsO$_6$. Our neutron diffraction, muon spin relaxation and ac-susceptibility measurements reveal two antiferromagnetic (AFM) phases on cooling from room temperature down to 2 K. In the first AFM phase, with transition temperature $T_{\mathrm{N}}=108$ K, cobalt (3$d^7$, $S=3/2$) and osmium (5$d^2$, $S=1$) moments fluctuate dynamically, while their \textit{average} effective moments undergo long-range order. In the second AFM phase with $T_{\mathrm{N}}=67$ K, cobalt moments first becom…
Doped perovskite cobaltites (e.g., La$_{1-x}$Sr$_x$CoO$_3$) have been extensively studied for their spin-state physics, electronic inhomogeneity, and insulator-metal transitions. Ferromagnetically-interacting spin-state polarons emerge at low $x$ in the phase diagram of these compounds, eventually yielding long-range ferromagnetism. The onset of long-range ferromagnetism ($x \approx 0.18$) is substantially delayed relative to polaron percolation ($x \approx 0.05$), however, generating a troubling inconsistency. Here, Monte-Carlo simulations of a disordered classical spin model are used to esta…
We study the ultrafast phonon response of mixed-valence perovskite Cs$_2$Au$_2$I$_6$ using pump-probe spectroscopy under high-pressure in a diamond anvil cell. We observed a remarkable softening and broadening of the Au - I stretching phonon mode with both applied pressure and photoexcitation. Using a double-pump scheme we measured a lifetime of the charge transfer excitation into single valence Au$^{2+}$ of less than 4 ps, which is an indication of the local character of the Au$^{2+}$ excitation. Furthermore, the strong similarity between the pressure and fluence dependence of the phonon soft…
The magnetic and magnetotransport properties of the oxygen deficient perovskites, SrCo1-xMxO3-d with M = Nb and Ru, were investigated. Both Nb- and Ru-substituted cobaltites are weak ferromagnets, with transition temperatures Tm of 130-150 K and 130-180 K, respectively, and both exhibit a spin glass behavior at temperatures below Tf = 80-90 K. It is demonstrated that there exists a strong competition between ferromagnetism and spin glass state, where Co4+ induces ferromagnetism, whereas Nb or Ru substitution at the cobalt sites induces magnetic disorder, and this particular magnetic behavior i…
The oxygen-exchange behavior has been studied in half-doped manganese and cobalt perovskite oxides. We have found that the oxygen diffusivity in Gd_{0.5}Ba_{0.5}MnO_{3-δ} can be enhanced by orders of magnitude by inducing crystallographic ordering among lanthanide and alkali-earth ions in the A-site sublattice. Transformation of a simple cubic perovskite, with randomly occupied A-sites, into a layered crystal GdBaMn_2O_{5+x} (or isostructural GdBaCo_2O_{5+x} for cobalt oxide) with alternating lanthanide and alkali-earth planes reduces the oxygen bonding strength and provides disorder-free chan…
We investigate the excitation spectrum of strongly correlated sodium cobaltate within a realistic many-body description beyond dynamical mean-field theory (DMFT). At lower doping around $x$=0.3, rather close to Mott-critical half-filling, the single-particle spectral function of Na$_x$CoO$_2$ displays an upper Hubbard band which is captured within DMFT. Momentum-dependent self-energy effects beyond DMFT become dominant at higher doping. Around a doping level of $x\sim 0.67$, the incoherent excitations give way to finite-energy spin-polaron excitations in close agreement with optics experiments…
Neutron scattering has been used to study the nature of the ferromagnetic transition in a single crystal of the perovskite La0.7Ca0.3MnO3. Diffuse scattering from lattice polarons develops as the Curie temperature is approached from below, along with short range polaron correlations that are consistent with stripe formation. Both the scattering due to the polaron correlations and the anomalous quasielastic component in the magnetic fluctuation spectrum maximize very close to T_C, in a manner remarkably similar to the resistivity, indicating that they have a common origin.
Many transition metal oxides (TMOs) are Mott insulators due to strong Coulomb repulsion between electrons, and exhibit metal-insulator transitions (MITs) whose mechanisms are not always fully understood. Unlike most TMOs, minute doping in CaMnO3 induces a metallic state without any structural transformations. This material is thus an ideal platform to explore band formation through the MIT. Here, we use angle-resolved photoemission spectroscopy to visualize how electrons delocalize and couple to phonons in CaMnO3. We show the development of a Fermi surface where mobile electrons coexist with h…
We study the excitonic phase and low-energy excitation spectra of perovskite cobalt oxides. Constructing the five-orbital Hubbard model defined on the three-dimensional cubic lattice for the $3d$ bands of Pr$_{0.5}$Ca$_{0.5}$CoO$_3$, we calculate the excitonic susceptibility in the normal state in the random-phase approximation (RPA) to show the presence of the instability toward excitonic condensation. Based on the excitonic ground state with a magnetic multipole obtained in the mean-field approximation, we calculate the dynamical susceptibility of the excitonic phase in the RPA and find that…
The nature of the polarons in the optimally doped colossal magnetoresistive (CMR) materials La0.7Ba0.3MnO3 (LBMO) and La0.7Sr0.3MnO3 (LSMO) is studied by elastic and inelastic neutron scattering. In both materials, dynamic nanoscale polaron correlations develop abruptly in the ferromagnetic state. However, the polarons are not able to lock-in to the lattice and order, in contrast to the behavior of La0.7Ca0.3MnO3. Therefore ferromagnetic order in LBMO and LSMO survives their formation, explaining the conventional second order nature of the ferromagnetic--paramagnetic transition. Nevertheless, …
We have investigated cobaltite relatives of the layered perovskite cuprates and nickelates, Pr$_{2-x}$Ca$_x$CoO$_4$ ($0.39 \leq x \leq 0.73$) and La$_{2-x}$Sr$_x$CoO$_4$ ($x = 0.61$), using elastic neutron scattering. We have discovered doping-dependent incommensurate short-range ordering of charges and magnetic moments, which in cobaltites occur in the range of heavy doping, $ 0.5 \lesssim x \lesssim 0.75$. The charge order exists already at room temperature and shows no change on cooling. The incommensurability of its propagation vector, ${\bf Q}_c = (ε_c,0,l)$, roughly scales with the conce…
Inspired by the strong experimental evidence for the coexistence of localized and itinerant charge carriers close to the metal-insulator transition in the ferromagnetic phase of colossal magnetoresistive manganese perovskites, for a theoretical description of the CMR transition we propose a two-phase scenario with percolative characteristics between equal-density polaron and Zener band-electron states. We find that the subtle balance between these two states with distinctly different electronic properties can be readily influenced by varying physical parameters, producing various ``colossal'' …
The electronic and magnetic states in doped perovskite cobaltites, (La, Sr)CoO_3, are studied in the numerically exact diagonalization method on Co_2O_{11} clusters. For realistic parameter values, it is shown that a high spin state and an intermediate spin state coexist in one-hole doped clusters due to strong p-d mixing. The magnetic states in the doped cobaltites obtained in the calculation explain various experimental results.
Muon spin relaxation measurements are reported on samples of dimethylammonium metal formates containing magnetic divalent nickel, cobalt, manganese, and copper ions. These hybrid organic-inorganic perovskites exhibit weak ferromagnetism and are, apart from the copper system, multiferroics with well separated magnetic and antiferroelectric transitions. We use muons to follow the sublattice magnetization, observing the effect of the spin reorientation transitions below TN and the criticality approaching TN. The multiferroic samples have three-dimensional antiferromagnetic interactions, but the c…
Electron-boson interaction is fundamental to a thorough understanding of various exotic properties emerging in many-body physics. In photoemission spectroscopy, photoelectron emission due to photon absorption would trigger diverse collective excitations in solids, including the emergence of phonons, magnons, electron-hole pairs, and plasmons, which naturally provides a reliable pathway to study electron-boson couplings. While fingerprints of electron-phonon/-magnon interactions in this state-of-the-art technique have been well investigated, much less is known about electron-plasmon coupling, a…
Recent studies exposed many remarkable properties of layered cobaltates NaxCoO2. Surprisingly, many-body effects have been found to increase at sodium-rich compositions of NaxCoO2 where one expects a simple, nearly free motion of the dilute S=1/2 holes doped into a band insulator NaCoO2. Here we discuss the origin of enigmatic correlations that turn a doped NaCoO2 into a strongly correlated electronic system. A minimal model including orbital degeneracy is proposed and its predictions are discussed. The model is based on a key property of cobalt oxides - the spin-state quasidegeneracy of CoO6 …
Ruthenates provide comprehensive platform to study a plethora of novel properties, such as quantum magnetism, superconductivity and magnetic fluctuation mediated metal-insulator transition. In this article, we provide an overview of quantum mechanical phenomenology in calcium ruthenium oxide with varying compositions. While the stochiometric composition of CaRuO$_{3}$ exhibits non-Fermi liquid behavior with quasi-criticality, chemically doped compounds depict prominent signatures of quantum magnetic fluctuations at low temperature that in some cases are argued to mediate in metal-insulator tra…
Bismuth perovskites ABiO$_3$ (A = Sr, Ba) host a variety of peculiar phenomena including bond-disproportionated insulating phases and high-temperature superconductivity upon hole doping. While the mechanisms underlying these phenomena are still debated, off-diagonal electron-phonon ($e$-ph) coupling originating from the modulation of the orbital overlaps has emerged as a promising candidate. Here, we employ classical Monte Carlo simulations to study a semiclassical three-orbital model with off-diagonal $e$-ph interactions. We demonstrate the existence of a (bi)polaron correlations that persist…
Two different kinds of metal transition oxides have been studied for their large thermopower values. The first one corresponds to the Tl-based misfit cobaltite which is a hole-doped metal. We demonstrate that the partial Bi-substitution for Tl in this phase induces an increase of the room temperature (RT) thermopower (TEP) value. Same result is obtained with the new Pb_{1/3}SrCoO_{3+delta} misfit corresponding to the Tl complete replacement by lead. Simultaneously, the T dependence of their resistivity exhibits a re-entrance below 70-90K where a large negative magnetoresistance is observed. Ma…
We argue that in lightly hole doped perovskite-type Mn oxides the holes (Mn$^{4+}$ sites) are surrounded by nearest neighbor Mn$^{3+}$ sites in which the occupied $3d$ orbitals have their lobes directed towards the central hole (Mn$^{4+}$) site and with spins coupled ferromagnetically to the central spin. This composite object, which can be viewed as a combined orbital-spin-lattice polaron, is accompanied by the breathing type (Mn$^{4+}$) and Jahn-Teller type (Mn$^{3+}$) local lattice distortions. We present calculations which indicate that for certain doping levels these orbital polarons may …
Recent research suggests that the charge carriers in the paramagnetic state of the magnetoresistive manganites are small polarons. Here we report studies of the oxygen-isotope effects on the intrinsic resistivity and thermoelectric power in several ferromagnetic manganites. The precise measurements of these isotope effects allow us to make a quantitative data analysis. Our results do not support a simple small-polaron model, but rather provide compelling evidence for the presence of small immobile bipolarons, i.e., pairs of small polarons. Since the bipolarons in the manganites are immobile, t…
The effects of Co addition on the chemical and electronic structure of PbTiO$_3$ were explored both by theory and through experiment. Cobalt was incorporated to PbTiO$_3$ during sol gel process. The XRD data of the compounds confirmed the perovskite structure for the pure samples. The XRD lines broadened and showed emerging cubic-like features as the Co incorporation increased. The changes in the XRD pattern were interpreted as double perovskite structure formation. $^{207}$Pb NMR measurements revealed a growing isotropic component in the presence of Co. In line with the experiments, DFT calcu…
The effect of cobalt and nickel substitutions for manganese on the physical properties of the perovskite manganite La1.2Bi0.8Mn2-x(Ni/Co)xO6+d, with x = 0.0-0.8, has been investigated. It is observed that the ferromagnetism is enhanced, TC being increased from 103 K for the parent compound (x = 0.0) to 178 K for Ni-phase, and to 181 K for the Co-phase (x = 0.8). Moreover, the systems remain insulating and depict relatively large values of magnetoresistance effect at low temperatures (up to 67 % at 90K and 70 kOe, for x = 0.0 phase). These phenomena are interpreted by means of electronic phase …
We explore the competiton of doped holes and defects that leads to the loss of orbital order in vanadate perovskites. In compounds such as La$_{1-{\sf x}}$Ca$_{\,\sf x}$VO$_3$ spin and orbital order result from super-exchange interactions described by an extended three-orbital degenerate Hubbard-Hund model for the vanadium $t_{2g}$ electrons. Long-range Coulomb potentials of charged Ca$^{2+}$ defects and $e$-$e$ interactions control the emergence of defect states inside the Mott gap. The quadrupolar components of the Coulomb fields of doped holes induce anisotropic orbital rotations of degener…
