Spin State of Co<Superscript>3+</Superscript> Ions in Layered GdBaCo<Subscript>2</Subscript>O<Subscript>5.5</Subscript> Cobaltite in the Paramagnetic Phase

A new scheme interpreting the changes in the spin state of Co³⁺ ions in GdBaCo₂O_5.5 in the course of the metal–insulator transition is proposed. The transition occurs gradually within a wide (~100 K) temperature range. The changes in the spin state of Co³⁺ ions are revealed using the data on the linear thermal expansion. In the metallic state, less than one-half of Co³⁺ ions are in the high-spin (HS, S = 2) state in octahedra, whereas the remaining ions are in the low-spin (LS, S = 0) state. The transition to the nonmetallic state occurs owing to the transformation of the HS state to the LS state in octahedra and to the transformation of some part of LS Со3+ in pyramids to the intermediate-spin (IS, S = 1) state.     

Covalence-induced stabilization of an intermediate-spin state and the magnetic susceptibility of LaCoO<Subscript>3</Subscript>

The energies of terms with spins S = 0, 1, 2 have been found using exact diagnoalization of the multielectron Hamiltonian of a multiband pd model for the CoO₆ cluster. Co (e _g orbital)-O hops, which form the covalent σ bond, are shown to decrease the energy of the state (IS) with an intermediate spin (S = 1) as compared to the energy of the state (LS) with a low spin (S = 0). An analogue of the Tanabe-Sugano diagram that takes into account the covalence of the CoO₆ cluster is constructed. The state with S = 1 is shown to be a ground state at certain model parameters. An increase in temperature is established to decrease the crystal field and, thus, favors the transition of the ground state from LS to IS at T = 100 K and the transition of the IS ground state to a state (HS) with a high spin (S = 2) at T = 550 K. The magnetic susceptibility of LaCoO₃ is calculated with allowance for the LS, IS, and HS states and for the fact that the HS state exhibits threefold orbital degeneracy of the t _2g shell, which results in an effective orbital moment L = 1 and the importance of spin-orbit interaction. The behavior of this magnetic susceptibility agrees well with the experimental x(T) dependence of LaCoO₃.     

Magnetoresistance of LaCoO<Subscript>3</Subscript> and an insulator-metal transition induced in it by a high magnetic field

The transformation of the band structure of LaCoO₃ in the applied magnetic field has been theoretically studied. If the field is below its critical value B _C ≈ 65 T, the dielectric band gap decreases with the field, thus giving rise to negative magnetoresistance that is highest at T ≃ 300–500 K. The critical field is related to the crossover between the low- and high-spin terms of Co³⁺ ions. The spin crossover results in an insulator-metal transition induced by an increase in the magnetic field.     

LaCoO3中自旋态转变现象的超声研究

测量了LaCoO₃单相多晶样品的纵波与横波超声声速和衰减随温度的变化关系, 在材料的自 旋态转变温度附近（≈90K），纵波声速出现明显的软化并伴随一个尖锐的衰减峰，但是在 横波的测量中却没有出现类似的超声异常，分析认为LaCoO₃在90K附近的自旋态 转变是由于Co³⁺离子是从低自旋态(LS,t⁶_2ge⁰ _g)转变到中等自旋态(IS,t⁵ _2ge¹_g )，而不是高等自旋态(HS,t⁴_2ge²_g).随着温度的升高，在 200K附近纵波和横波测量上都观察到一个伴随着微小声速软化的宽大的衰减峰，这可能是随 机分布的IS态Co³⁺离子的Jahn-Teller效应导致的局域晶格扭曲所造成的. 关键词： 超声声速与衰减 自旋态转变 Jahn-Teller效应     

Quantum chemical study of Co<Superscript>3+</Superscript> spin states in LaCoO<Subscript>3</Subscript>

Ab initio quantum-chemical cluster calculations are performed for the perovskite LaCoO₃. The main concern is to calculate the energy level ordering of different spin states of Co³⁺, which is an issue of great controversy for many years. The calculations performed for the trigonal lattice structure at T = 5 K and 300 K, with the structural data taken from experiment, display that the low-spin (LS, S = 0) ground state is separated from the first excited high-spin (HS, S = 2) state by a gap <100 meV, while the intermediate-spin (IS, S = 1) state is located at much higher energy ≈0.5 eV. We suggest that the local lattice relaxation around the Co³⁺ ion excited to the HS state and the spin-orbit coupling reduce the spin gap to a value ~10 meV. Coupling of the IS state to the Jahn-Teller local lattice distortion is found to be rather strong and reduces its energy position to a value of 200 ?\div 300 meV. Details of the quantum-chemical cluster calculation procedure and the obtained results are extensively discussed and compared with those reported earlier by other authors.     

Electronic structure,magnetic properties,and mechanism of the insulator–metal transition in LaCoO<Subscript>3</Subscript> taking into account strong electron correlations

The electronic structure of LaCoO₃ at finite temperatures is calculated using the LDA+GTB method taking into account strong electron correlations and possible spin crossover upon an increase in temperature. Gap states revealed in the energy spectrum of LaCoO₃ reduce the dielectric gap width upon heating; this allowed us to describe the insulator-metal transition observed in this compound at T = 500–600 K. The temperature dependence of the magnetic susceptibility with a peak at T ≈ 100 K is explained by the Curie contribution from thermally excited energy levels of the Co³⁺ ion. At high temperatures, the Pauli contribution from a band electron is added and the total magnetization of LaCoO₃ is considered as the sum M _tot = M _loc + M _band. The second term describes the band contribution appearing as a result of the insulator-metal transition and facilitating the emergence of a high-temperature anomaly in the magnetic susceptibility of LaCoO₃.     

Lattice structure and magnetization of LaCoO<Subscript>3</Subscript> thin films

We investigate the structure and magnetic properties of thin films of the LaCoO₃ compound. Thin films are deposited by pulsed laser deposition on various substrates in order to tune the strain from compressive to tensile. Single-phase (001) oriented LaCoO₃ layers were grown on all substrates despite large misfits. The tetragonal distortion of the films covers a wide range from -2% to 2.8%. Our LaCoO₃ films are ferromagnetic with Curie temperature around 85 K, contrary to the bulk. The total magnetic moment is below 1μ _B /Co³⁺, a value relatively small for an exited spin-state of the Co³⁺ ions, but comparable to values reported in literature. A correlation of strain states and magnetic moment of Co³⁺ ions in LaCoO₃ thin films is observed.     

Pressure induced antiferromagnet-ferromagnet transition in La<Subscript>0.5</Subscript>Ba<Subscript>0.5</Subscript>CoO<Subscript>2.8</Subscript> cobaltite

The anion deficient cobaltite La_0.5Ba_0.5CoO_2.8 with theformal cobalt valence state close to 3+ has been studied as function of pressure up to6.5 GPa at different temperatures by neutron powder diffraction. At ambient pressure thecrystal structure of this compound has cubic symmetry (space group Pm3?m) and is found to become antiferromagnetic withT _N close to 250 K. Applied pressure inducesa gradual transition from the antiferromagnetic into a ferromagnetic state through a mixedmagnetic state. The transition is not accompanied by obvious changes in the macroscopiccrystal symmetry. It is suggested that the magnetic ground state strongly depends on theunit cell volume and that the transition is associated with a spin state crossover of thecobalt ions whereas the formal Co³⁺/Co⁴⁺ ratio is less importantthan expected following the double exchange scenario for the appearance offerromagnetism.     

Investigation of a Spin Transition in a LaCoO<Subscript>3</Subscript> Single Crystal by the Method of X-Ray Magnetic Circular Dichroism at the Cobalt <Emphasis Type="Italic">K</Emphasis>- and <Emphasis Type="Italic">L</Emphasis><Subscript>2,3</Subscript>-Edges

Spin transitions of cobalt ions in LaCoO₃ single crystals have been studied by the method of X-ray magnetic circular dichroism (XMCD) at the K- and L_2,3-edges of Co³⁺ ions. The orbital momentum of cobalt ions obtained for the K-edge at the 3d level in the region of the spin transition in the temperature range from 25 to 120 K increases by a factor of approximately 1.6, whereas the slope of the magnetization curve value in the same temperature range and magnetic field increases by a factor of more than 10. XMCD experiments at the cobalt L_2,3-edges demonstrate gradual growth of the ratio of the orbital momentum to the spin one L/S from 0.48 to 0.53 in the temperature range from 60 K to 120 K.     

Temperature dependence of the spin state of a Co3+ Ion in RCoO3 (R = La,Gd) cobaltites

Changes in the spin state of Co³⁺ ions in LaCoO₃ and GdCoO₃ compounds are studied through the use of the temperature dependence of the magnetic susceptibility and the modified crystal field theory. It is shown that the spin subsystem of Co³⁺ ions in LaCoO₃ and GdCoO₃ undergoes the spin-crossover type transition between the high-spin (S = 2) and low-spin (S = 0) states without any contribution of the intermediate-spin state (S = 1).     

Description of the pressure-induced insulator-metal transition in BaCoS2 within the LDA + DMFT approach

The pressure-induced insulator-metal transition in paramagnetic sulfide BaCoS₂ at a temperature of 370 K has been described for the first time using the combination of the local electron density approximation and the dynamic mean field theory (LDA + DMFT). Based on the analysis of the spectral functions of Co 3d orbitals, the local magnetic moments of Co, and the frequency dependence of the imaginary part of the self-energy, the existence of the insulator-metal transition for 97% of the BaCoS₂ unit cell volume at normal pressure has been established. Simultaneously, the high-to-low spin magnetic transition of Co²⁺ ions occurs.     

Magnetically induced phase transitions in LaCoO<Subscript>3</Subscript> in fields of up to 500 T

The differential magnetization of LaCoO₃ in magnetic fields of up to 500 T has been measured at a temperature of 4.2 K. The magnetization curve reveals several features which suggest a complex pattern of the transition of LaCoO₃ from the low-spin state to the high-spin state. The magnetic moment starts to grow in fields above 50 T to reach a plateau in the 130–240-T region, after which the magnetic moment continues to rise up to saturation in fields ∼500 T.     

Spin transition and thermal expansion in the layered cobaltite GdBaCo<Subscript>2</Subscript>O<Subscript>5.5</Subscript>

The electrical conductivity and thermal expansion coefficient of GdBaCo₂O_5.5 samples have been measured in order to reveal the mechanism of the metal-insulator transition in cation-ordered cobaltites RBaCo₂O_5.5 (where R is a rare-earth element) and its relation to the change in the spin state of cobalt ions. It has been established that the unit cell volume considerably increases upon the transition to the metallic state at T _MI ≈ 360–365 K and that the thermal expansion exhibits anomalies (which are two orders of magnitude weaker) due to the ferromagnetic and antiferromagnetic orderings. The data obtained confirm that the spin transition in Co³⁺ ions actually proceeds simultaneously with the metal-insulator transition and excludes the possibility of stepwise spin transitions occurring at lower temperatures.     

Magnetic ground state and the spin-state transitions in YBaCo<Subscript>2</Subscript>O<Subscript>5.5</Subscript>

The crystal and magnetic structure of the perovskite-like, oxygen deficient cobalt oxide YBaCo₂O_5.5 has been studied by means of neutron and X-ray diffraction in the 10–300 K temperature range. The magnetic ground state is characterized by a coexistence of two distinct antiferromagnetic phases. In the first one, the ionic moments of high-spin Co³⁺ ions in the pyramidal sites are ordered in a spiral arrangement, while octahedral sites are non-magnetic due to presence of low-spin Co³⁺ ions. The arrangement in the second phase is collinear of the G-type, with non-zero moments both in pyramidal (high-spin Co³⁺ ions) and octahedral sites (presumably a mixture of the low- and high-spin states). With increasing temperature, at 260–300 K, the system develops a gradual structural transformation, which is associated with appearance of spontaneous magnetic moment. This process is related to a thermally induced reversion of low- and high-spin states at the octahedral sites to the intermediate-spin Co³⁺ states, resulting in an insulator-metal transition at T_C ≈ T_IM ≈ 295 K.     

Neutron diffraction investigation of a metamagnetic transition in the Tb<Subscript>0.1</Subscript> Tm<Subscript>0.9</Subscript>Co<Subscript>2</Subscript> compound

The Tb_0.1Tm_0.9Co₂ compound is investigated using neutron diffraction. It is shown that this compound undergoes an irreversible band metamagnetic transition induced by an external magnetic field. The magnetization of the Co sublattice increases from 0.2 to 0.6 μ_B. The critical field strength is approximately equal to 1 T at temperatures of 1.8 and 4.0 K. As the temperature increases, the effect of the magnetic field on the magnetic state of the sample weakens and, at 25 K, no noticeable changes are observed in an external field of 0.75 T. The metamagnetic transition at 1.8 K is accompanied by the disappearance of rhombohedral distortions and brings about a lattice expansion by approximately 1%.     

Paramagnetic-ferromagnetic and insulator-metal phase transitions in La<Subscript>0.88</Subscript>MnO<Subscript>2.95</Subscript>

We present the results a study of structure by neutron diffraction and data on the magnetic properties (linear and nonlinear (second and third order) susceptibilities) of polycrystalline La_0.88MnO_2.95. This compound exhibits an insulator-metal (IM) phase transition at T _IM ≈ 253 K (above the Curie temperature, T _C ≈ 244 K) and reveals colossal magnetoresistance. The crystal structure is found to be rhombohedral, and the space group is R3c. Analysis of magnetic properties shows that at T* ≈ 258 K > T _C , isolated paramagnetic clusters occur in the paramagnetic matrix; their concentration increases upon cooling. We observed no noticeable differences between the temperature evolution of the clustered state of this manganite with its insulator-metal transition and in the insulator La_0.88MnO_2.91. Possible scenarios of the paramagnet-ferromagnet and I-M transitions in a self-organized clustered structure are discussed.     

Phase separation of the spin system in the La<Subscript>0.93</Subscript>Sr<Subscript>0.07</Subscript>MnO<Subscript>3</Subscript> crystal

The magnetic state of the manganite La_0.93Sr_0.07MnO₃ in the range 4.2–290 K was studied using elastic neutron scattering. The magnetic state of this compound was found to occupy a particular place in the La_1?xSr_xMnO₃ solid-solution system, in which the antiferromagnetic type of order (LaMnO₃, T_N=139.5 K) switches to ferromagnetic ordering (La_0.9Sr_0.1MnO₃, T_C=152 K) with increasing x. In the transition state, this compound contains large-scale spin configurations of two types. A fractional crystal volume of about 10% is occupied by regions of the ferromagnetic phase with an average linear size of 200 Å, while the remainder of the crystal is a phase with a nonuniform canted magnetic structure. Arguments are presented for the phase separation of the La_0.93Sr_0.07MnO₃ spin system being accounted for by Mn⁴⁺ ion ordering.     

Valence and magnetic states of impurity iron ions in the La<Subscript>0.75</Subscript>Sr<Subscript>0.25</Subscript>Co<Subscript>0.98</Subscript>Fe<Subscript>0.02</Subscript>O<Subscript>3</Subscript> perovskite

The local magnetic and valence states of impurity iron ions in the rhombohedral La_0.75Sr_0.25Co_0.98 ⁵⁷Fe_0.02O₃ perovskite were studied using Mössbauer spectroscopy in the temperature range 87–293 K. The Mössbauer spectra are described by a single doublet at 215–293 K. The spectra contained a paramagnetic and a ferromagnetic component at 180–212 K and only a broad ferromagnetic sextet at T < 180 K. The results of the studies showed that, over the temperature range 87–295 K, the iron ions are in a single (tetrahedral) state with a valence of +3. In the temperature range 180–212 K, two magnetic states of Fe³⁺ ions were observed, one of which is in magnetically ordered microregions and the other, in paramagnetic microregions; these states are due to atomic heterogeneity. In the magnetically ordered microregions in the temperature range 87–212 K, the magnetic state of the iron ions is described well by a single state with an average spin S = 1.4 ± 0.2 and a magnetic moment μ(Fe) = 2.6 ± 0.4μ _B .     

Switching from unusual to usual ferromagnetism in “112” LnBaCo2O5.50±δ: By calcium doping

The effect of calcium doping on the magnetic and transport properties of the intermediate size lanthanide cobaltites of the type Ln_1−xCa_xBaCo₂O_5.50±δ (Ln=Y, Gd, Eu and Sm) has been investigated for 0?x?0.2. The substitution of Ln by calcium induces a large expansion of the ferromagnetic state in the whole temperature range below T_C. The unusual trend of the decrease in T_C with the increase in Ln size in the undoped parent oxides becomes opposite in the calcium doped samples. Such an unusual behavior of the ferromagnetic T_C in the parent compounds is explained on the basis of thermally activated hole-mediated ferromagnetic coupling between the high-spin cobalt ions. The ferromagnetic state of the Ca-doped samples originates from the Co³⁺–O–Co⁴⁺ superexchange interaction, where Co⁴⁺ emerges from the disproportionation mechanism of the cobalt Co³⁺ into Co²⁺ and Co⁴⁺. However, the Ca-doping does not significantly affect the metal–insulator transition, which is associated with the structural change and not related to the spin state transition.     

High-resolution spectroscopy of HoFe<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> crystal: a study of phase transitions

The transmission spectra of HoFe₃(BO₃) multiferroic single crystals are studied by optical Fourier-transform spectroscopy at temperatures of 1.7–423 K in polarized light in the spectral range 500–10 000 cm^–1 with a resolution up to 0.1 cm^–1. A new first-order structural phase transition close to the second-order transition is recorded at T_c = 360 K by the appearance of a new phonon mode at 976 cm^–1. The reasons for considerable differences in T_c for different samples of holmium ferroborate are discussed. By temperature variations in the spectra of the f–f transitions in the Ho³⁺ ion, we studied two magnetic phase transitions, namely, magnetic ordering into an easy-plane structure as a second-order phase transition at T_N = 39 K and spin reorientation from the ab plane to the c axis as a first-order phase transition at T_SR = 4.7 ± 0.2 K. It is shown that erbium impurity in a concentration of 1 at % decreases the spin-reorientation transition temperature to T_SR = 4.0 K.