Orbital ordering in frustrated Jahn-Teller systems with 90 degrees exchange

We show that superexchange interactions in frustrated Jahn-Teller systems with transition metal ions connected by the 90 degrees metal-oxygen-metal bonds (e.g., NaNiO2, LiNiO2, and ZnMn2O4) are much different from those in materials with the 180 degrees bonds. In the 90 degrees -exchange systems spins and orbitals are decoupled: the spin exchange is much weaker than the orbital one and it is ferromagnetic for all orbital states. Though the mean-field orbital ground state is strongly degenerate, quantum orbital fluctuations select particular ferro-orbital states. We explain the orbital and magnetic ordering observed in NaNiO2 and show that LiNiO2 is not a spin-orbital liquid.     

Optical and magnetic characterisation of Co3+ and Ni3+ in LaAlO3: interplay between the spin state and Jahn-Teller effect

The coordination, the electronic structures and the spin of the ground state of Ni(3+) (3d(7)) and Co(3+) (3d(6)) introduced as impurities in LaAlO(3) are investigated through optical spectroscopy and magnetic measurements. The unusual trivalent valence state in both transition-metal ions was stabilised via a sol-gel process followed by high oxygen pressure treatments. We show that the crystal-field strength at the nearly O(h) transition-metal site in LaAlO(3) locates Ni(3+) and Co(3+) near the spin state crossover, yielding a low-spin ground state in both cases. We analyse how the interplay between the Jahn-Teller (JT) effect and the spin state affects the magnetic moment of the ion and its temperature dependence. The optical spectra reveal a JT effect associated with a low-spin ground state in Ni(3+) and with a thermally populated high-spin low-lying first excited state in Co(3+). The corresponding JT distortions are derived from structural correlations. We conclude that the JT effect is unable to stabilise the intermediate spin state in Co(3+). A low-spin ground state in thermal equilibrium with a high-spin low-lying first excited state is detected in diluted Co(3+)-doped LaAlO(3). These results are compared with those obtained in the parent pure compounds LaNiO(3) and LaCoO(3).     

Impurities in noncubic crystals: stabilization mechanisms for Jahn-Teller ions in layered perovskites

Mechanisms responsible for the local geometry around Jahn-Teller impurities in K2NiF4 type lattices are shown to be different from those generating the warping in cubic crystals. The present density functional theory calculations reveal that the elastic anisotropy of the host lattice (visible for closed shell impurities) and the electric field created by the rest of lattice ions upon active electrons make it possible to have d(9) ions in an elongated geometry but with a A(1g) ground state. The puzzling difference between equilibrium geometries for Cu2+ and Ni+ in layered perovskites can reasonably be understood.     

Nickel impurity-induced enhancement of the pseudogap of cuprate high-T(c) superconductors

The influence of magnetic Ni and nonmagnetic Zn impurities on the normal-state pseudogap (PG) in the c-axis optical conductivity of (Sm,Nd)Ba(2){Cu(1-y)(Ni,Zn)(y)}(3)O(7-delta) crystals was studied by spectral ellipsometry. We find that these impurities, which strongly suppress superconductivity, have a profoundly different impact on the PG. Zn gives rise to a gradual and inhomogeneous PG suppression while Ni strongly enhances the PG. Our results challenge theories that relate the PG either to precursor superconductivity or to other phases with exotic order parameters, such as flux phase or d-density wave states, that should be suppressed by potential scattering. The apparent difference between magnetic and nonmagnetic impurities instead points towards an important role of magnetic correlations in the PG state.     

Thermoelectric power of HoBaCo2O5.5: possible evidence of the spin blockade in cobaltites

Thermoelectric power measurements have been performed for an ordered oxygen-deficient perovskite, HoBaCo2O5.5, in which the alternative layers of CoO6 octahedra and of [CoO(5)](2) bipyramids are occupied by Co3+ species. The T-dependent Seebeck coefficient S shows a clear change of the conduction regime at the metal-insulator (MI) transition (T(MI) approximately 285 K). The sign change of S from S<0 to S>0 can be explained assuming that a spin state transition occurs at T(MI). In the metallic state, Co2+ e(g) electrons are moving in a broad band on the background of high or intermediate spin Co3+ species. In contrast, the insulating behavior may result from the Co3+ spin state transition to a low-spin Co3+ occurring in the octahedra. In this phase the transport would occur by hopping of the low-spin Co(4+)t(2g) holes, whereas the high-spin Co2+ electrons become immobilized due to a spin blockade.     

Theoretical characterization of the ground and optically excited states of alpha'-NaV2O5

The character of the ground and optically excited states was investigated by quantum chemical calculations. We propose a rung ground state with V 3d(1)(xy)-O 2p(1)(y)-V 3d(1)(xy) character, instead of the conventional picture of one unpaired electron shared by 2 V ions. The unpaired electron on O is low-spin coupled to the V d electrons and spin density is predicted to be localized on vanadium. The absorption peak at 0.9 eV is assigned to a state with similar orbital occupations but a different spin coupling scheme, resulting in spin density localized on the bridging oxygen.     

Ground state properties of S = 1 antiferromagnetic chain systems studied by ESR

Electron spin resonance (ESR) was used to study the ground state properties of two kinds of spin (S) one Heisenberg antiferromagnetic chain systems, namely a uniform chain system (HAUC), which is well known as the Haldane system, and a bond alternating chain system (HABA). To investigate and compare the features of the ground state, two nickel chain compounds doped with non-magnetic Zn²⁺ impurities were studied. The HAUC was modelled with Ni(1,3-pn)₂(μ-NO₂)(ClO₄)(1,3-pn = 1,3-propanediamine), abbreviated as NINO, while the HABA was modelled with Ni(333-tet)(μ-NO₂)(ClO₄) (333-tet = bis-(3-aminopropyl)-1,3-propanediamine), abbreviated as NTENP. Both systems have a singlet ground state with an excitation gap. The ground state of NINO approximates well to the valence bond solid state, thus producing S = 1/2 spins at the sites neighbouring the impurities. The angular dependence of the ESR signals of NINO:Zn is explained by the anisotropy of the g tensor for spin 1/2. On the other hand, the ground state of NTENP is expected to be in the singlet dimer phase based on the ratio of alternating bond strengths. In this case, it is expected that the S = 1 spins will appear at the sites neighbouring the impurities without forming the singlet dimer. From ESR studies of NTENP:Zn was observed the triplet state (S = 1), induced by the impurity doping, which is consistent with the above picture.     

Influence of divalent cationic impurities on plasticity of AgCl

The hardening effect of Mg²⁺, Ca²⁺, Sr²⁺, Cd²⁺ and Ba²⁺ impurities in polycrystalline AgCl was investigated. With exception of Mg²⁺ the hardening effect of the impurities decreases with increasing atomic number (atomic weight). The hardening effects of Mg²⁺ and Ca²⁺ are expressively stronger than those of the three remaining impurities. Approximately linear dependence of the stress at the beginning of plastic deformation on the impurity concentration was found. Possible causes of the different hardening effects of the divalent impurities are discussed.     

Orbital frustration at the origin of the magnetic behavior in LiNiO2

We report on the ESR, magnetization, and magnetic susceptibility measurements performed over a large temperature range, from 1.5 to 750 K, on high-quality stoichiometric LiNiO2. We find that this compound displays two distinct temperature regions where its magnetic behavior is anomalous. With the help of a statistical model based on the Kugel'-Khomskii Hamiltonian, we show that below T(of) approximately 400 K, an orbitally frustrated state characteristic of the triangular lattice is established. This then gives a solution to the long-standing controversial problem of the magnetic behavior in LiNiO2.     

Tracer impurity diffusion in single-crystal rutile (TiO2−x)

By means of the radioactive-tracer sectioning technique, the tracer diffusion of the impurity ions, ⁴⁶Sc, ⁵¹Cr, ⁵⁴Mn, ⁵⁹Fe, ⁶⁰Co, ⁶³Ni and ⁹⁵Zr, in rutile single crystals was measured as functions of crystal orientation, temperature, oxygen partial pressure and Al impurity content. The diffusion coefficients are very sensitive to the electric charge of the impurity ions. Divalent impurities (e.g., Co and Ni) diffuse extremely rapidly in TiO₂, compared to cation self-diffusion, and exhibit an extreme anisotropy in diffusion behavior, divalent-impurity diffusion parallel to the c-axis is much larger than it is perpendicular to the c-axis. Trivalent impurity ions (Sc and Cr) and tetravalent impurity ions (Zr) diffuse similar to cation self-diffusion, both as functions of temperature and oxygen partial pressure. The divalent impurity ions Co and Ni apparently diffuse as interstitial ions along open channels parallel to the c-axis. The results suggest that Sc, Cr and Zr ions diffuse by an interstitialcy mechanism involving the simultaneous and cooperative migration of tetravalent interstitial titanium ions and the tracer-impurity ions. Iron ions diffuse both as divalent and as trivalent ions. The impurity diffusion as functions of oxygen partial pressure and Al-impurity content are consistent with calculations of point-defect concentrations in rutile.     

Strongly correlated electrons in the [Ni(hmp)(ROH)X]4 single molecule magnet: a DFT+U study

The single-molecule magnet [Ni(hmp)(MeOH)Cl]4 (hmp denotes the anion of 2-hydroxymethylpyridine and Me denotes methyl) is studied using both density functional theory (DFT) and the DFT+U method, and the results are compared. By incorporating a Hubbard-U like term for both the nickel and oxygen atoms, the experimentally determined ground state is successfully obtained, and the exchange coupling constants derived from the DFT+U calculation agree with experiment very well. The results show that the nickel 3d and oxygen 2p electrons in this molecule are strongly correlated, and thus the inclusion of on site Coulomb energies is crucial to obtaining the correct results.     

ZnSiF66H2O∶Fe2+晶体光谱结构的杨特勒效应和电子顺磁共振g因子

研究了过渡金属络合物ZnSiF66H2O∶Fe2+晶体光谱结构的杨特勒效应和电子顺磁共振g因子。由单晶的中子衍射方法得到ZnSiF66H2O∶Fe2+的晶体结构,这种结构可以用SiF2-6和Zn(H2O)++∶Fe2+两个离子来描述。而局域三角对称的Zn(H2O)++∶Fe2+离子反映了这种晶体的主要光谱性质。利用不可约张量的理论构成了晶体场和自旋轨道相互作用哈密顿矩阵和电子顺磁共振理论公式,求出了晶体ZnSiF66H2O∶Fe2+中Fe2+离子的电子顺磁共振零场分裂参量(D,F-a)及g因子,并研究了低自旋3L态对电子顺磁共振零场分裂参量的贡献是不能忽略的,而对g因子的贡献是非常小的,并理论计算了它的晶体结构,证实了杨特勒效应的存在,理论计算的结果与实验值是相符的。     

锂电池正极材料Li(Co,Ni)O2化合物的第一性原理研究

锂离子电池以其高能量存储密度和优良的循环性能而受到广泛关注, 尤其是其正极材料成为储能材料领域的研究热点.本文采用基于密度泛函理论的第一性原理方法对LiCoO2,LiNiO2和Li(Co0.5Ni0.5)O2化合物的晶体结构、电子结构、化学键合特性进行了研究. 结果表明：Li(Co0.5Ni0.5)O2化合物中主要是氧和过渡金属之间成键, 锂原子对晶体总态密度贡献很少. Ni/Co混合后将导致Li(Co0.5Ni0.5)O2中Co的3d轨道和O的2p轨道之间成键得以加强.     

Optical properties of the surface transition-metal structures in fluoride ionic crystals and peculiarities of their formation during thermal diffusion

The possibility of forming surface films with an elevated concentration of an impurity metal during high-temperature diffusion has been analyzed for a wide series of ionic crystals: LiF with Co, Ni, Mg, Ca, Ba, and Sr impurities; NaF with Co, Mn, Mg, Ca, and Sr; MgF₂ with Co and Ni; and CaF₂ with Co. It is established that films are formed only on alkali halide crystals with impurities of transition metals and are not formed on alkaline earth fluorides with transition metals, as well as on alkali halide crystals activated with other divalent cationic impurities. The dynamics of the increase and decrease in the intensity of centers related to impurity-vacancy dipoles during thermal diffusion is shown. The mechanisms of film formation are explained in terms of the features of growth and structure of ionic crystals with cationic impurities and on the basis of isomorphism rules.     

Magnetic behaviour of isolated Fe and Ni ions measured directly after implantation into II-VI-semiconductors

Abstract

The local magnetic behaviours of isolated Fe and Ni impurities in the II-VI semiconductors ZnS and ZnTe have been studied directly after recoil implantation. From the measured magnetic properties, which are detected by the observation of the perturbed angular distribution, orbital contributions to the hyperfine field as well as contributions from spin magnetism are found to be present at both impurities. The interpretations on the basis of the intermediate ligand field model suggest that Fe and Ni ions are found to exist in 2+ and in 1+ states and that electronic excitations may play a significant role even microseconds after the implantation.     

锂电池正极材料Li(Co,Ni)O2化合物的第一性原理研究

锂离子电池以其高能量存储密度和优良的循环性能而受到广泛关注, 尤其是其正极材料成为储能材料领域的研究热点.本文采用基于密度泛函理论的第一性原理方法对LiCoO2,LiNiO2和Li(Co0.5Ni0.5)O2化合物的晶体结构、电子结构、化学键合特性进行了研究. 结果表明：Li(Co0.5Ni0.5)O2化合物中主要是氧和过渡金属之间成键, 锂原子对晶体总态密度贡献很少. Ni/Co混合后将导致Li(Co0.5Ni0.5)O2中Co的3d轨道和O的2p轨道之间成键得以加强.     

Formation of F-centers in Kcl-Rbcl solid solutions with Sr2+ and OH− impurities

The kinetics of F-center formation are studied in crystals of KCl-RbCl. solid solutions, both in the pure state and with Sr²⁺ and OH^– impurities. The crystals were irradiated by electrons at 1.2 MeV at room temperature. The initial stage of coloration in crystals that have been purified of divalent cation impurities is the same as that of pure crystals; only when Sr²⁺ is introduced is this stage sharply accelerated. The efficiency of F-center formation in the second stage of coloration is significantly smaller in purified crystals than in pure crystals.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii Fizika, No. 7, pp. 38–41, July, 1971.     

Selective photoswitching of the binuclear spin crossover compound {[Fe(bt)(NCS)2]2(bpm)} into two distinct macroscopic phases

The low-spin (LS-LS, S = 0) diamagnetic form of the binuclear spin crossover complex {[Fe(bt)(NCS)(2)](2)(bpm)} was selectively photoconverted into two distinct macroscopic phases at different excitation wavelengths (1342 or 647.1 nm). These long-lived metastable phases have been identified, respectively, as the symmetry-broken paramagnetic form (HS-LS, S = 2) and the antiferromagnetically coupled (HS-HS, S = 0) high-spin form of the compound. The selectivity may be explained by the strong coupling of the primary excited states to the paramagnetic state.     

Effect of quenching on the electrical conductivity of doped KCl crystals

Electrical conductivity and optical absorption of divalent cation and anion doped KCl crystals have been measured before and after quenching from 750 °C. The conductivity after quenching is found to decrease in undoped and cation doped crystals while it increases in the anion doped crystals. This is due to higher coagulation rate of cation impurities as compared to anion impurities. Since the divalent impurities diffuse in the form of impurity-vacancy complexs, the higher mobility of cation vacancies (which form dipoles with divalent cation impurities) accounts for the higher aggregation rate of the cation impurities. The aggregation rate, during annealing after quenching, has also been found to depend on concentration.The author is indebted to Prof. H. N.Bose for helpful discussions. Thanks are also due to Dr. M. L.Mukherjee for providing the crystals.     

Magnetization and electron spin resonance of Fe impurities in (TMTSF)2AsF6: magnetic-field-dependent interaction between impurity spins and spin-density waves

A new spin-density-wave (SDW) system with magnetic impurities (TMTSF)₂(AsF₆)_1−x(FeCl₄)_x was prepared and its magnetic properties were studied by means of magnetization and electron-spin-resonance measurements. The anisotropic g-value and comparison of the Fe concentration with the Curie constant indicate that the Fe³⁺ ions are in a low-spin state. We also found that the magnetization curve of the impurity spins in this compound shows an anomalous behavior. This behavior can be explained if one assumes a field-dependent magnetic interaction between the Fe³⁺ spins and the SDW moment. We suppose that the field dependence of the SDW pinning potential is responsible for this phenomenon.