A wide family of cobalt oxides of formulation (Pr,Ln,Ca)CoO3 (Ln being a lanthanide) exhibits a coupled valence and spin-state transition (VSST) at a temperature T*, which involves two concomitant modifications: (i) a change in the spin state of Co3+ from low-spin (T < T*) to a higher spin-state (T > T*), and (ii) a change in the valence state of Pr, from a mixed Pr4+/Pr3+ state (T < T*) to a purely trivalent state (T > T*), accompanied by an equivalent charge transfer within the Co3+/Co4+ subsystem. In the present paper, the VSST taking place in (Pr0.7Sm0.3)0.7Ca0.3CoO3 at T* = about 90 K is investigated by magnetization and heat capacity measurements. First, we quantitatively characterized the jumps in magnetic susceptibility (khi) and entropy (S) around T*. Then, these values were compared to those calculated as a function of the variations in the population of the different cationic species involved in the VSST. X-ray absorption spectroscopy experiments recently showed that the higher spin state above T* should be regarded as an inhomogeneous mixture between low-spin (LS) and high-spin (HS) states. In the frame of this description, we demonstrate that the jumps in both khi and S can be associated to the same change in the Co3+ HS content around T*. This result lends further support to the relevance of the LS/HS picture for the VSST, challenging the currently dominant interpretation based on the occurrence of an intermediate-spin (IS) state of Co3+ above T*.
(Pr0.7Sm0.3)0.7Ca0.3CoO3 belongs to a class of cobalt oxides undergoing a first-order transition (T* close to 90 K) associated to a coupled change in the valence and spin-state degrees of freedom. The Curie-Weiss regime present around room temperature (T >> T*) was analysed in detail to address the controversial issue of the cobalt spin states above the transition. This magnetic investigation indicates that the Co4+ are in an intermediate spin-state, while the Co3+ are in a mixed state combining low-spin and high-spin states. These results are discussed with respect to the literature on relate…
We report a successful tuning of Co valence state in cobalt oxyhydrate superconductor via a facile post reduction using NaOH as reducing agent. The change in Co valence was precisely determined by measuring the volume of the released oxygen. The possible hydronium-incorporation was greatly suppressed in concentrated NaOH solution, making the absolute Co valence determinable. As a result, an updated superconducting phase diagram was obtained, which shows that the superconducting transition temperature increases monotonically with increasing Co valence in a narrow range from +3.58 to +3.65.
We present a study of the magnetic susceptibility of La_2-xSr_xCoO_4 single crystals in a doping range 0.3<=x<=0.8. Our data shows a pronounced magnetic anisotropy for all compounds. This anisotropy is in agreement with a low-spin ground state (S=0) of Co^3+ for x>=0.4 and a high-spin ground state (S=3/2) of Co^2+. We compare our data with a crystal-field model calculation assuming local moments and find a good description of the magnetic behavior for x>=0.5. This includes the pronounced kinks observed in the inverse magnetic susceptibility, which result from the anisotropy and low-energy exci…
Magnetic properties of the Co valence tautomers are considered in wide range of magnetic field and temperature. Particularly, a model of the first order structural phase transition accompanied by a magnetic moment jump is proposed. The phase diagrams of the phase transition on a B-T plane (B is magnetic field and T is temperature) are calculated for four ligand types. Dependence of the critical magnetic field on physical characteristics known from experiments (transition temperature at the absense of magnetic field, entropy change per formula unit, energy difference between two phases) is foun…
We report on susceptibility measurements in the strongly correlated layered cobalt oxide [BiBa0.66K0.36O2]CoO2, which demonstrate the existence of a magnetic quantum critical point (QCP) governing the electronic properties. The investigated low frequency susceptibility displays a scaling behavior with both the temperature T and the magnetic field B ranging from the high-T non-Fermi liquid down to the low-T Fermi liquid. Whereas the inferred scaling form can be discussed within the standard framework of the quantum critical phenomena, the determined critical exponents suggest an unconventional …
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…
We have investigated the temperature dependence of the magnetic susceptibility $χ(T)$ of rare-earth cobaltites RCoO$_3$ (R= La, Pr, Nd, Sm, Eu) in the temperature range $4.2-300$ K and also the influence of hydrostatic pressure up to 2 kbar on their susceptibility at fixed temperatures $T=78 $ and 300 K. The specific dependence $χ(T)$ observed in LaCoO$_3$ and the anomalously large pressure effect (d ln $χ$/d$P\sim -100$ Mbar$^{-1}$ for $T = 78$ K) are analyzed in the framework of a two-level model with energy levels difference $Δ$. The ground state of the system is assumed to be nonmagnetic w…
Using 23Na NMR measurements on sodium cobaltates at intermediate dopings (0.44<=x<=0.62), we establish the qualitative change of behavior of the local magnetic susceptibility at x*=0.63-0.65, from a low x Pauli-like regime to the high x Curie-Weiss regime. For 0.5<=x<=0.62, the presence of a maximum T* in the temperature dependence of the susceptibility shows the existence of an x-dependent energy scale. T_1 relaxation measurements establish the predominantly antiferromagnetic character of spin correlations for x<x*. This contradicts the commonly assumed uncorrelated Pauli behavior in this x r…
We have examined cobalt based valence tautomer molecules such as Co(SQ)$_2$(phen) using density functional theory (DFT) and variational configuration interaction (VCI) approaches based upon a model Hamiltonian. Our DFT results extend earlier work by finding a reduced total energy gap (order 0.6 eV) between high temperature and low temperature states when we fully relax the coordinates (relative to experimental ones). Futhermore we demonstrate that the charge transfer picture based upon formal valence arguments succeeds qualitatively while failing quantitatively due to strong covalency between …
We present X-ray spectroscopic evidence for the evolution of valence-specific spin states and tetragonal distortions in single-layer cobaltates. Measurements of Co $L_3$-edge resonant inelastic X-ray scattering reveal the $t_{2g}$ electronic structure of Co for hole-doped La$_{2-x}$Sr$_x$CoO$_4$ ($x$ = 0.5, 0.7 and 0.8). As the Sr-doping $x$ increases, the tetragonal splitting of the $t_{2g}$ states of high-spin Co$^{2+}$ decreases, whereas that of low-spin Co$^{3+}$ increases and the fraction of high-spin Co$^{3+}$ increases. The results enable us to clarify the origin of the change of magnet…
Macroscopic magnetization, muon spin rotation (muSR), and NMR measurements were carried out to study magnetism in the Na1CoO2 cobaltate. Using SQUID measurements, Na1CoO2 is shown to have a bulk magnetic susceptibility much lower and flatter than that of NaxCoO2 with x=0.7-0.9. In fact, muSR yields a signal of mostly nonmagnetic origin, which is attributed to the x=1 phase. The intrinsic cobalt spin susceptibility corresponding to this x=1 phase is measured using Na NMR. It is indeed found to be almost zero, in agreement with a low-spin 3+ charge state of all cobalt atoms. This single state of…
The novel spin-chain cobalt oxide Sr5Pb3CoO12 [P-62m, a = 10.1093(2) A and c = 3.562 51(9) A at 295 K] is reported. Polycrystalline sample of the compound was studied by neutron diffraction (at 6 and 295 K) and magnetic susceptibility measurements (5 to 390 K). The cobalt oxide was found to be analogous to the copper oxide Sr5Pb3CoO12, which is comprised of magnetic-linear chains at inter-chain distance of 10 A. Although the cobalt oxide chains (mu_eff of 3.64 mu_B per Co) are substantially antiferromagnetic (theta_W = -38.8 K), neither low-dimensional magnetism nor long-range ordering has bee…
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 systematically analyze the influence of the superconducting gap symmetry and the electronic structure on the dynamical spin susceptibility in superconducting Na_xCoO_2$\cdot y$H_2O within a three different models: the single a_{1g}-band model with nearest-neighbor hoppings, the realistic three-band t_{2g}-model with, and without e'_g pockets present at the Fermi surface. We show that the magnetic response in the normal state is dominated by the incommensurate antiferromagnetic spin density wave fluctuations at large momenta in agreement with experimental temperature dependence of the spin-l…
Various samples of sodium cobalt oxyhydrate with relatively large amounts of Na$^{+}$ ions were synthesized by a modified soft-chemical process in which a NaOH aqueous solution was added in the final step of the procedure. From these samples, a superconducting phase diagram was determined for a section of a cobalt valence of $\sim$+3.48, which was compared with a previously obtained one of $\sim$+3.40. The superconductivity was significantly affected by the isovalent exchanger of Na$^{+}$ and H$_{3}$O$^{+}$, rather than by variation of Co valence, suggesting the presence of multiple kinds of F…
We study valence fluctuations in the extended Anderson model on two-dimensional Penrose lattice, using the real-space dynamical mean-field theory combined with the continuous-time Monte Carlo method. Calculating $f$-electron number, $c$-$f$ spin correlations, and magnetic susceptibility at each site, we find site-dependent formations of the singlet state and valence distribution at low temperatures, which are reflected by the quasiperiodic lattice structure. The bulk magnetic susceptibility is also addressed.
Doping of the band insulator FeS$_2$ with Co on the Fe site introduces a small density of itinerant carriers and magnetic moments. The lattice constant, AC and DC magnetic susceptibility, magnetization, and specific heat have been measured over the $0\le x\le 0.085$ range of Co concentration. The variation of the AC susceptibility with hydrostatic pressure has also been measured in a small number of our samples. All of these quantities show systematic variation with $x$ including a paramagnetic to disordered ferromagnetic transition at $x=0.007\pm 0.002$. A detailed analysis of the changes wit…
Magnetic susceptibility, heat capacity, and electrical resistivity measurements have been carried out on single crystals of the intermediate valence compounds Yb2Rh3Ga9 and Yb2Ir3Ga9. These measurements reveal a large anisotropy due apparently to an interplay between crystalline electric field (CEF) and Kondo effects. The temperature dependence of magnetic susceptibility can be modelled using the Anderson impurity model including CEF within an approach based on the Non-Crossing Approximation.
We show theoretically that the nuclear spin-lattice relaxation rate (T_1T)^{-1} and the spin susceptibility exhibit divergent behaviors toward zero temperature at the quantum critical point (QCP) of the first-order valence transition. Remarkable enhancement in (T_1T)^{-1} and the spin susceptibility is induced by valence fluctuations even at the valence-crossover temperature far away from the QCP. This mechanism well explains peculiar behaviors observed recently in YbAuCu_4 and also gives a systematic explanation for YbXCu_4 for X=In, Au, Ag, Tl, and Pd from the viewpoint of the closeness to t…
We present a comparative study of CoO2 layers in the Bi-misfit and NaxCoO2 cobaltates. Co NMR measures the intrinsic susceptibility of the Co layers and is not affected by spurious contributions. At low dopings where room-temperature thermopower (TEP) is large, Curie-Weiss susceptibilities are observed in both materials. But NMR and muSR experiments find neither charge nor spin order down to low temperatures in Bi-misfit, in contrast to the case of NaxCoO2. This demonstrates that metallicity, charge and magnetic orders are specific of the Na layers in NaxCoO2 whereas strong correlations are ge…
We present a single crystal study of low temperature magnetism and transport in Sm$Tr_2$Al$_{20}$ ($Tr =$ Ti, V and Cr). Strong valence fluctuation is manifested as Kondo effects including a large Sommerfeld coefficient $γ$, a weak temperature dependence of magnetic susceptibility and a $-\ln T$ dependent resistivity. All the systems order antiferromagnetically at $T_{\rm N}=$ 6.4 K (Ti), 2.3 K (V) and 1.8 K (Cr). Systematic change in the susceptibility, specific heat, and resistivity indicates that stronger $c$-$f$ hybridization in SmV$_2$Al$_{20}$ and SmCr$_2$Al$_{20}$ than in SmTi$_2$Al$_{2…
We have investigated the low temperature specific heat properties as a function of magnetic field in the strongly correlated layered cobalt oxide [BiBa$_{0.66}$K$_{0.36}$O$_2$]CoO$_2$. These measurements reveal two kinds of magnetic field dependent contributions in qualitative agreement with the presence of a previously inferred magnetic Quantum Critical Point (QCP). First, the coefficient of the low temperature T$^3$ behavior of the specific heat turns out to sizeably decrease near a magnetic field consistent with the critical value reported in a recent paper. In addition, a moderate but sign…
We present a detailed study of the temperature evolution of the crystal structure, specific heat, magnetic susceptibility and resistivity of single crystals of the paradigmatic valence-fluctuating compound EuIr$_2$Si$_2$. A comparison to stable-valent isostructural compounds EuCo$_2$Si$_2$ (with Eu$^{3+}$), and EuRh$_2$Si$_2$, (with Eu$^{2+}$) reveals an anomalously large thermal expansion indicative of the lattice softening associated to valence fluctuations. A marked broad peak at temperatures around 65-75 K is observed in specific heat, susceptibility and the derivative of resistivity, as t…
We report on a member of the spin-disordered honeycomb lattice antiferromagnet in a quasi-one-dimensional cobaltate Ba_3Co_2O_6(CO_3)_0.7. Resistivity exhibits as semimetallic along the face-sharing CoO6 chains. Magnetic susceptibility shows strongly anisotropic Ising-spin character with the easy axis along the chain due to significant spin-orbit coupling and a trigonal crystal field. Nevertheless, ^135Ba NMR detects no indication of the long-range magnetic order down to 0.48 K. Marginally itinerant electrons possess large entropy and low-lying excitations with a Wilson ratio R_W = 116, which …
We found a new cobalt oxide (CaOH)1.14CoO2 by utilizing the high-pressure technique. X-ray and electron diffraction studies revealed that the compound has layer structure which consists of CdI2-type CoO2 layers and rock-salt-type double CaOH atomic layers. The two subcells have incommensurate periodicity along the a-axis, resulting in modulated crystal structure due to the inter-subcell interaction. The structural modulation affects carrier conduction through the potential randomness. We found that the two-dimensional (2-D) variable-range hopping (VRH) regime with hole conduction is dominant a…
Visualization of Co 3d high- and low-spin states via valence electron density
RIKEN Center for Emergent Matter Science (CEMS)（RIKEN 新兴物质科学中心）；Department of Advanced Materials Science, The University of Tokyo（东京大学先进材料科学系）；Japan Synchrotron Radiation Research Institute (JASRI)（日本同步辐射研究所）；Center for Basic Research on Materials (CBRM), National Institute for Materials Science (NIMS)（国立材料研究所基础材料研究中心）；UGC-DAE Consortium for Scientific Research（UGC-DAE 科学研究联盟）；International Center for Synchrotron Radiation Innovation Smart, Tohoku University（东北大学国际同步辐射创新智能中心）
A quantum critical behavior of the magnetic susceptibility was observed in a quasicrystal containing ytterbium. At the same time, a mixed-valence feature of Yb ions was reported, which appears to be incompatible with the magnetic instability. We derive the magnetic susceptibility by expressing the quasiperiodicity as the distributed hybridization strength between Yb 4f and conduction electrons. Assuming a wide distribution of the hybridization strength, the most f electrons behave as renormalized paramagnetic states in the Kondo or mixed-valence regime, but a small number of f moments remain u…
Here we report the magnetic properties of the layered cobalt oxide system, LixCoO2, in the whole range of Li composition, 0 <= x <= 1. Based on dc-magnetic susceptibility data, combined with results of 59Co-NMR/NQR observations, the electronic phase diagram of LixCoO2 has been established. As in the related material NaxCoO2, a magnetic critical point is found to exist between x = 0.35 and 0.40, which separates a Pauli-paramagnetic and a Curie-Weiss metals. In the Pauli-paramagnetic regime (x <= 0.35), the antiferromagnetic spin correlations systematically increase with decreasing x. Neverthele…
We present the crystal growth as well as the structural, chemical and physical chracterization of SmRh$_2$Si$_2$ single crystals. Their ground state is antiferromagnetic, as indicated by the behaviour of the magnetic susceptibility and the specific heat at the second order phase transition observed at T$_{\rm N}$ = 64 K. The Sommerfeld coefficient is small and similar to that of LuRh$_2$Si$_2$ with $γ_0\approx$ J/(molK$^2$). Susceptibility measurements show no Curie-Weiss behaviour at high temperatures which is a consequence of the large Van-Vleck contribution of the excited multiplets of Sm$^…
We have investigated the valence, spin, and orbital state of the Co ions in the one-dimensional cobaltate Ca3Co2O6 using x-ray absorption and x-ray magnetic circular dichroism at the Co-L2,3 edges. The Co ions at both the octahedral Co_oct and trigonal Co_trig sites are found to be in a 3+ state. From the analysis of the dichroism we established a low-spin state for the Co_oct and a high-spin state with an anomalously large orbital moment of 1.7 muB at the Co3+ trig ions. This large orbital moment along the c-axis chain and the unusually large magnetocrystalline anisotropy can be traced back t…
We present a combined experimental and theoretical x-ray absorption spectroscopy (XAS) study of the new class of cobaltates YBaCo4O7 and YBaCo3MO7 (M= Al, Fe). The focus is on the local electronic and magnetic properties of the transition metal ions in these geometrically frustrated kagome compounds. For the mixed valence cobaltate YBaCo4O7, both the Co2+ and Co3+ are found to be in the high spin state. The stability of these high spin states in tetrahedral coordination is compared with those in the more studied case of octahedral coordination. For the new compound YBaCo3FeO7, we find exclusiv…
We present the study of magnetization, thermal expansion, specific heat, resistivity, and a.c. susceptibility of (Pr$_{1-y}$Eu$_y$)$_{0.7}$Ca$_{0.3}$CoO$_3$ cobaltites. The measurements were performed on ceramic samples with $y = 0.12 - 0.26$ and $y = 1$. Based on these results, we construct the phase diagram, including magnetic and spin-state transitions. The transition from the low- to intermediate-spin state is observed for the samples with $y > 0.18$, whereas for a lower Eu-doping level, there are no spin-state transitions, but a crossover between the ferromagnetic and paramagnetic states …
We investigate the effect of Dzyaloshinskii-Moriya interactions on the low temperature magnetic susceptibility for a system whose low energy physics is dominated by short-range valence bonds (singlets). Our general perturbative approach is applied to specific models expected to be in this class, including the Shastry-Sutherland model of the spin-dimer compound SrCu_2(BO_3)_2 and the antiferromagnetic Heisenberg model of the recently discovered S=1/2 kagome compound ZnCu_3(OH)_6Cl_2. The central result is that a short-ranged valence bond phase, when perturbed with Dzyaloshinskii-Moriya interact…
CaBaCo4O7 represents a new class of ferrimagnets whose structure is built up of CoO4 tetrahedra only, similarly to other members LnBaCo4O7 of the 114 series, forming an alternate stacking of kagome and triangular layers. Neutron powder diffraction reveals, that this compound exhibits the largest distortion within the 114 series, characterized by a strong buckling of the kagome layers. Differently from all other members it shows charge ordering, with Co2+ sitting on two sites (Co2, Co3) and mixed valent cobalt Co3+/Co2+L sitting on two other sites (Co1, Co4). The unique ferrimagnetic structure …
Exploring Low-Dimensional Magnetism in Cobalt Vanadates, ${A}$CoV$_{2}$O$_{7}$~(${A}$~=~Ca, Sr) : Crystal Growth and Magnetic Properties of Effective Spin-1/2 Zigzag Chains
We present a dynamical mean field theory study of the valence transition ($f^{14} \to f^{13}$) in elemental, metallic Yb under pressure. Our calculations reproduce the observed valence transition as reflected in the volume dependence of the $4f$ occupation. The transition is accelerated by heating, and suggests quasiparticle or Kondo-like structure in the spectra of the trivalent end state, consistent with the early lanthanides. Results for the local charge fluctuations and susceptibility, however, show novel signatures uniquely associated with the valence transition itself, indicating that Yb…
We report electrical resistivity, ac magnetic susceptibility and X-ray absorption spectroscopy measurements of intermediate valence YbNi$_{3}$Ga$_{9}$ under pressure and magnetic field. We have revealed a characteristic pressure-induced Yb valence crossover within the temperature-pressure phase diagram, and a first-order metamagnetic transition is found below $P_{\rm c}$ $\sim$ 9 GPa where the system undergoes a pressure-induced antiferromagnetic transition. As a possible origin of the metamagnetic behavior, a critical valence fluctuation emerging near the critical point of the first-order val…
We investigate the behavior of the periodic Anderson model in the presence of $d$-$f$ Coulomb interaction ($U_{df}$) using mean-field theory, variational calculation, and exact diagonalization of finite chains. The variational approach based on the Gutzwiller trial wave function gives a critical value of $U_{df}$ and two quantum critical points (QCPs), where the valence susceptibility diverges. We derive the critical exponent for the valence susceptibility and investigate how the position of the QCP depends on the other parameters of the Hamiltonian. For larger values of $U_{df}$, the Kondo re…
CaCo$_{2-y}$As$_2$ is an unusual itinerant magnet with signatures of extreme magnetic frustration. The conditions for establishing magnetic order in such itinerant frustrated magnets, either by reducing frustration or increasing electronic correlations, is an open question. Here we use results from inelastic neutron scattering and magnetic susceptibility measurements and density functional theory calculations to show that hole doping in Ca(Co$_{1-x}$Fe$_{x}$)$_{2-y}$As$_{2}$ suppresses magnetic order by quenching the magnetic moment while maintaining the same level of magnetic frustration. The…
The momentum transfer dependence of the magnetic form factor associated with the quasielastic spectral component in the dynamic magnetic response of intermediate valence SmB$_{6}$ has been measured using inelastic neutron scattering on a double-isotope ($^{154}$Sm, $^{11}$B) single crystal. The experimental dependence differs qualitatively from those obtained earlier for the inelastic signals, as well as from the field-induced magnetic form factor of SmB$_{6}$ obtained by polarized neutron diffraction. This observation is interpreted by specifically considering the Curie-type contributions to …
We report on the unconventional magnetism in the cubic B-site ordered double perovskite Ba2YMoO6, using AC and DC magnetic susceptibility, heat capacity and muSR. No magnetic order is observed down to 2 K while the Weiss temperature is ~ -160 K. This is ascribed to the geometric frustration in the lattice of edge-sharing tetrahedra with orbitally degenerate Mo5+ s=1/2 spins. Our experimental results point to a gradual freezing of the spins into a disordered pattern of spin-singlets, quenching the orbital degeneracy while leaving the global cubic symmetry unaffected, and providing a rare exampl…
Bulk studies have revealed a first-order valence phase transition in Ba$_2$PrRu$_{1-x}$Ir$_x$O$_6$ ($0.10 \le x \le 0.25$), which is absent in the parent compounds with $x = 0$ (Pr$^{3+}$) and $x =1$ (Pr$^{4+}$), which exhibit antiferromagnetic order with transition temperatures $T_{\rm N} = 120$ and 72 K, respectively. In the present study, we have used magnetization, heat capacity, neutron diffraction, inelastic neutron scattering and x-ray absorption measurements to investigate the nature of the Pr ion in $x =0.1$. The magnetic susceptibility and heat capacity of $x =0.1$ show a clear sign …
We present a neutron scattering investigation of Ce1-xYxAl3 as a function of chemical pressure, which induces a transition from heavy-fermion behavior in CeAl3 (TK=5 K) to a mixed-valence state at x=0.5 (TK=150 K). The crossover can be modeled accurately on an absolute intensity scale by an increase in the k-f hybridization, Vkf, within the Anderson impurity model. Surprisingly, the principal effect of the increasing Vkf is not to broaden the low-energy components of the dynamic magnetic susceptibility but to transfer spectral weight to high energy.
The magnetic, electric and thermal properties of the ($Ln_{1-y}$Y$_{y}$)$_{0.7}$Ca$_{0.3}$CoO$_3$ perovskites ($Ln$~=~Pr, Nd) were investigated down to very low temperatures. The main attention was given to a peculiar metal-insulator transition, which is observed in the praseodymium based samples with $y=0.075$ and 0.15 at $T_{M-I}=64$ and 132~K, respectively. The study suggests that the transition, reported originally in Pr$_{0.5}$Ca$_{0.5}$CoO$_3$, is not due to a mere change of cobalt ions from the intermediate- to the low-spin states, but is associated also with a significant electron tran…
Above 40K, the magnetic susceptibility of the heavy Fermion spinel LiV2O4 has many features in common with those of geometrically frustrated magnetic insulators, while its room temperature resistivity comfortably exceeds the Mott-Regel limit. This suggests that local magnetic moments, and the underlying geometry of the pyrochlore lattice, play an important role in determining its magnetic properties. We extend a recently introduced tetragonal mean field theory for insulating pyrochlore antiferromagnets to the case where individual tetrahedra contain spins of different lengths, and use this as …
The intermediate valence compounds Yb2M3Ga9 (M = Rh, Ir) exhibit an anisotropic magnetic susceptibility. We report measurements of the temperature dependence of the 4f occupation number, nf(T), for Yb2M3Ga9 as well as the magnetic inelastic neutron scattering spectrum Smag at 12 and 300 K for Yb2Rh3Ga9. Both nf(T) and Smag were calculated for the Anderson impurity model with crystal field terms within an approach based on the non-crossing approximation. These results corroborate the importance of crystal field effects in these materials; they also suggest that Anderson lattice effects are impo…
We have compared by $^{23}$Na NMR and magnetic susceptibility the magnetic properties of oriented powder samples of Na$_{x}$CoO$_{2}$ compounds. The NMR spectra are found identical for various samples with nominal $0.50\leq x\leq 0.70,$ which establishes that the dominant phase has a single composition $x\approx 0.70$. Three Na sites are identified from their single valued quadrupole effects and magnetic shifts which implies a very definite order of the Na$^{+}$ ions and of the Co charges in the CoO$_{2}$ planes. The local susceptibility of the magnetic cobalt sites displays a large enhancemen…
Using numerical renormalization group method the temperature dependences of the magnetic susceptibility $χ(T)$ and specific heat $C(T)$ are obtained in the single-impurity Anderson model with inclusion of the $d-f$ Coulomb interaction. It is shown that the exciton effects owing to this interaction can change considerably the dependence $C(T)$ in comparison with the standard Anderson model at not too low temperatures, whereas the dependence $χ(T)$ remains universal. The renormalization of the effective hybridization parameter and $f$-level position, which is connected with the $d-f$ interaction…
We carried out AC magnetic susceptibility measurements and muon spin relaxation spectroscopy on the cubic double perovskite Ba2YMoO6, down to 50 mK. Below ~1 K the muon relaxation is typical of a magnetic insulator with a spin-liquid type ground state, i.e. without broken symmetries or frozen moments. However, the AC susceptibility revealed a dilute-spin-glass like transition below ~ 1 K. Antiferromagnetically coupled Mo5+ 4d1 electrons in triply degenerate t2g orbitals are in this material arranged in a geometrically frustrated fcc lattice. Bulk magnetic susceptibility data has previously bee…
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…
For describing the first-order isostructural valence phase transition in mixed valence compounds we develop a new approach based on the lattice Anderson model. We take into account the Coulomb interaction between localized f and conduction band electrons and two mechanisms of electron-lattice coupling. One is related to the volume dependence of the hybridization. The other is related to local deformations produced by f- shell size fluctuations accompanying valence fluctuations. The large f -state degeneracy allows us to use the 1/N expansion method. Within the model we develop a mean-field the…
Two-dimensional AKLT model on a honeycomb lattice has been shown to be a universal resource for quantum computation. In this valence bond solid, however, the spin interactions involve higher powers of the Heisenberg coupling $(\vec{S}_i \cdot \vec{S}_j)^n$, making these states seemingly unrealistic on bipartite lattices, where one expects a simple antiferromagnetic order. We show that those interactions can be generated by orbital physics in multiorbital Mott insulators. We focus on $t_{2g}$ electrons on the honeycomb lattice and propose a physical realization of the spin-$3/2$ AKLT state. We …
We report detailed dc magnetization, linear and non-linear ac susceptibility measurements on the hole doped disordered cobaltite La$_{0.5}$Ba$_{0.5}$CoO$_3$. Our results show that the magnetically ordered state of the system consists of coexisting non-ferromagnetic phases along with percolating ferromagnetic-clusters. The percolating ferromagnetic-clusters possibly undergo a 3D Hisenberg like magnetic ordering at the Curie temperature of 202(3) K. In between 202 and 220 K, the linear and non-linear ac susceptibility measurements show the presence of magnetic correlations even when the spontane…
We study experimentally and theoretically the effect of Eu doping and partial oxygen isotope substitution on the transport and magnetic characteristics and spin-state transitions in (Pr$_{1-y}$Eu$_y$)$_{0.7}$Ca$_{0.3}$CoO$_3$ cobaltites. The Eu doping level $y$ is chosen in the range of the phase diagram near the crossover between the ferromagnetic and spin-state transitions ($0.10 < y < 0.20$). We prepared a series of samples with different degrees of enrichment by the heavy oxygen isotope $^{18}$O, namely, containing 90%, 67%, 43%, 17%, and 0% of $^{18}$O. Based on the measurements of ac mag…
