Optical investigation of charge-transfer transitions in spinel Co3O4

Optical transitions in normal-spinel Co₃O₄ have been identified by investigating the variation of its optical absorption spectrum with the replacement of Co by Zn. Three optical-transition structures were located at about 1.65, 2.4, and 2.8 eV from the measured dielectric function of Co₃O₄ by spectroscopic ellipsometry. The variation of the absorption structures with the Zn substitution (Zn_xCo_3−xO₄) can be explained in terms of charge-transfer transitions involving d states of Co ions. The 1.65 eV structure is assigned to a d-d charge-transfer transition between the t_2g states of octahedral Co³⁺ ion and t₂ states of tetrahedral Co²⁺ ion, t_2g(Co³⁺)→t₂(Co²⁺). The 2.4 and 2.8 eV structures are interpreted as due to charge-transfer transitions involving the p states of O²⁻ ion: p(O²⁻)→t₂(Co²⁺) for the 2.4 eV absorption and p(O²⁻)→e_g(Co³⁺) for the 2.8 eV absorption. The observed gradual reduction of the 1.65 and 2.4 eV absorption strength with the increase of the Zn composition for Zn_xCo_3−xO₄ can be explained in terms of the substitution of the tetrahedral Co²⁺ sites by Zn²⁺ ions. The crystal-field splitting Δ_Oh between the e_g and the t_2g states of the octahedral Co³⁺ ion is estimated to be 2 eV.     

Spin-state transition, magnetic, electrical and thermal transport properties of the perovskite cobalt oxide Gd0.7Sr0.3CoO3

The magnetization, resistivity ρ, thermoelectric power (TEP) S, and thermal conductivity κ in perovskite cobalt oxide Gd_0.7Sr_0.3CoO₃ have been investigated systematically. Based on the temperature dependence of susceptibility χ_g(T) and Seebeck coefficient S(T), a combination of the intermediate-spin (IS) state for Co³⁺ and the low-spin (LS) state for Co⁴⁺ can be suggested. A metal-insulator transition (MIT) caused by the hopping of σ* electrons (localized or delocalized e_g electrons) from the IS Co³⁺ to the LS Co⁴⁺ is observed. Meanwhile, S(T) curve also displays an obvious phonon drag effect. In addition, based on the analysis of the temperature dependence of S(T) and ρ(T), the high-temperature small polaron conduction and the low-temperature variable-range-hopping conduction are suggested, respectively. As to thermal conduction κ(T), rather low κ values in the whole measured temperature range is attributed to unusually large local Jahn-Teller (JT) distortion of Co³⁺O₆ octahedra with IS state.     

Substitutional site of Co2+ ion in RbMgF3 crystal

The spin-Hamiltonian (SH) parameters (g factors g _//, g _⊥ and hyperfine structure constants A _//, A _⊥) for Co²⁺ ions at the trigonal Mg²⁺ (I) and Mg²⁺ (II) sites of RbMgF₃ crystal are calculated from the second-order perturbation formulas based on the cluster approach for 3d⁷ ions in trigonal symmetry. From the calculations, it is found that the calculated SH parameters for Co²⁺ ion at the Mg²⁺ (I) site are in poor agreement with, but those for Co²⁺ at the Mg²⁺ (II) site are close to, the experimental values. Therefore, we suggest that Co²⁺ in RbMgF₃ crystal substitutes for Mg²⁺ (II) ion. The results are discussed.     

Sur l'evolution des proprietes physiques de la perovskite GdCoO3 entre 77 et 1200 K

GdCoO₃, which has the GdFeO₃ structure, has been studied between 77 and 1200 K by D.T.A., X-ray diffraction, magnetic susceptibility, electric conductivity and thermoelectric power. All properties observed, although different from those of LaCoO₃, fit with the corresponding Goodenough localized electron model. With rising temperature cobalt ions pass progressively from a low-spin Co^III(t⁶_2ge_g⁰) state to a Co³⁺(t⁴_2ge_g²) high-spin state.     

Magnetic disorder induced enhanced magneto-resistance in La0.5Sr0.5Co1−xRuxO3

We observe a sharp increase in negative magneto-resistance ratio up to 40% for x=0.1, in La_0.5Sr_0.5Co_1−xRu_xO₃ which is due to the magnetic disorder induced by an anti-ferromagnetic interaction between Co and Ru ions. We also observe a metal to insulator and a ferromagnetic to anti-ferromagnetic transition for 0≤x≤0.3. Ruthenium (IV) ion disrupts an intermediate spin state of cobalt (Co³⁺:t_2g⁵e_g¹), forcing a double exchange mediated ferromagnetic state to an anti-ferromagnetic spin state for x≥0.2.     

Bulk and surface properties of spinel Co3O4 by density functional calculations

DFT calculations are employed to bulk and surface properties of spinel oxide Co₃O₄. The bulk magnetic structure is calculated to be antiferromagnetic, with a Co²⁺ moment of 2.631 μ_B in the antiferromagnetic state. There are three predicted electron transitions O(2p) → Co²⁺(t_2g) of 2.2 eV, O(2p) → Co³⁺(e_g) of 2.9 eV and Co³⁺(t_2g) → Co²⁺(t_2g) of 3.3 eV, and the former two transitions are close to the corresponding experimental values 2.8 and 2.4 eV. The naturally occurring Co₃O₄ (1 1 0) and (1 1 1) surfaces were considered for surface calculations. For ideal Co₃O₄ (1 1 0) surfaces, the surface relaxations are not significant, while for ideal Co₃O₄ (1 1 1) surfaces the relaxation of Co²⁺ cations in the tetrahedral sites is drastic, which agrees with the experiment observation. The stability over different oxygen environments for possible ideal and defect surface terminations were explored.     

Gyromagnetic ratio of the 2+ rotational state of184W and observation of a large hyperfine anomaly with respect to183Wg in iron

Theg-factor of the 2⁺ rotational state of¹⁸⁴W was redetermined by an IPAC measurement in an external magnetic field of 9.45 (5)T as: $$g_{2^ + } (^{184} W) = + 0.289(7).$$ In the evaluation the remeasured half-life of the 2⁺ state: $$T_{{1 \mathord{\left/ {\vphantom {1 2}} \right. \kern-\nulldelimiterspace} 2}} (2^ + ) = 1.251(12)ns$$ was used. TDPAC-measurements with a sample of carrierfree¹⁸⁴Re in high purity iron gave the hyperfine fields: $$B_{300 K}^{hf} (^{184} W_2 + \underline {Fe} ) = 70.1(21)T$$ and $$B_{40 K}^{hf} (^{184} W_{2^ + } \underline {Fe} ) = 71.8(22)T.$$ A comparison with the hyperfine field known from a spin echo experiment with¹⁸³W _g Fe leads to the hyperfine anomaly: $$^{184} W_{2^ + } \Delta ^{183} W_g = + 0.145(36).$$ The hyperfine splitting observed in a Mössbauer source experiment with another sample of carrierfree^184m Re in high purity iron indicates that the smaller splitting, measured previously by a Mössbauer absorber experiment is due to the high tungsten concentration in the absorber. The new value for theg-factor of the 2⁺ state together with the result of the Mössbauer experiment allow an improved calibration for our recent investigation of theg _R -factors of the 4⁺ and 6⁺ rotational states. The recalculated values are: $$g_{4^ + } (^{184} W) = + 0.293(23)$$ and $$g_{6^ + } (^{184} W) = + 0.299(43).$$ The remeasured 792-111 keVγ-γ angular correlation $$W(\Theta ) = 1 - 0.034(4) \cdot P_2 + 0.325(6) \cdot P_4 $$ gives for the mixing ratio of theK-forbidden 792keV transition: $$\delta ({{E2} \mathord{\left/ {\vphantom {{E2} {M1}}} \right. \kern-\nulldelimiterspace} {M1}}) = - \left( {17.6\begin{array}{*{20}c} { + 1.8} \\ { - 1.5} \\ \end{array} } \right).$$ A detailed investigation of the attenuation ofγ-γ angular correlations in liquid sources of¹⁸⁴Re and^184m Re revealed the reason for erroneous results of early measurements of the 2⁺ g _R -factor: The time dependence of the perturbation is not of a simple exponential type. It contains an unresolved strong fast component.     

Ground state of BaCoS2 as a set of energy-degenerate orbital-ordered configurations of Co2+ ions

The linear muffin-tin orbital method in the local density approximation (LDA + U) explicitly considering Coulomb correlations has been applied to calculate the electronic structure, magnetic moments, and parameters of the Heisenberg exchange interaction for cobalt ions in BaCoS₂. Five solutions close in total energy with various orbital ordering of Co²⁺ ions and almost identical spin magnetic moments μ = 2.32μ_B of the Co²⁺ ion 3d-shell have been found. The BaCoS₂ ground state can be considered as a set of energy-degenerate orbital-ordered configurations of Co²⁺ ions in the high-spin state.     

The ground state and EPR spectrum in monoclinic KY(WO4)2:Nd single crystal

The electron paramagnetic resonance (EPR) of Nd³⁺ ion in KY(WO₄)₂ single crystal was investigated at T=4.2 K using an X-band spectrometer. The observed resonance absorption represents the complex superposition of three spectra corresponding to neodymium isotopes with different nuclear momenta. The EPR spectrum is characterized by a strong g-factor anisotropy. The temperature dependences of the g-factor were caused by strong spin-orbit and orbit-lattice coupling. The resonance lines become broader as temperature increases due to the short spin-lattice relaxation time.     

Theg factor of the lowest 7+ state in100Rh and 6− state in104Rh

Theg-factor of the 7⁺ state in¹⁰⁰Rh withT _1/2=140(5) ns and of the 6^? state in¹⁰⁴Rh withT _1/2=47(3)ns has been measured by the time-differential perturbedγ-ray angular distribution method (TDPAD). The obtained values are +0.67(2) and +0.33(1) respectively. The two nuclei were populated with reactions induced by⁷Li on^96,100Mo at a bombarding energy of 30 MeV. Shell model calculations using effective single particle moments show that the 7⁺ state in¹⁰⁰Rh has mostly a πg _9/2 ? vd _5/2 configuration, while the main component of the 6^? state in¹⁰⁴Rh is the πg _9/2 ? vh _11/2.     

Doping induced spin state transition in Li<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>CoO<Subscript>2</Subscript> as studied by the GGA + DMFT calculations

The magnetic properties of Li _x CoO₂ for x = 0.94, 0.75, 0.66, and 0.51 are investigated within the method combining the generalized gradient approximation with dynamical mean field theory (GGA + DMFT). A delicate interplay between Hund’s exchange energy and t _2g ?e _g crystal field splitting is found to be responsible for the high-spin to low-spin state transition for Co⁴⁺ ions. The GGA + DMFT calculations show that the Co⁴⁺ ions at a small doping level adopt the high-spin state, while delithiation leads to an increase in the crystal field splitting and low-spin state becomes preferable. The Co³⁺ ions are found to stay in the low-spin configuration for any x values.     

Magnetic and ESR studies of Er3+ in lanthanum dihydride LaH2

Er³⁺ electron spin resonance ESR and magnetic susceptibility have been studied in metallic lanthanum dihydride host. The ESR spectrum contains a single asymmetrical line with g-factor g = 6.68 ± 0.05 close to that expected for Γ₇ as ground state. The experimental magnetic susceptibility was interpreted on the base of LLW cubic crystal field Hamiltonian. The best fit of the experimental data has been obtained for the following B₄ and B₆ crystal field parameters: B₄ = ?5.2 × 10^?3 K; B₆ = 3.8 × 10^?5 K which support the anionic-like character hydridic model of hydrogen atoms in this hydride.     

Theg-factor of the 2+ state of180W and quadrupole moment ratios observed for180W and180Hf by the Mössbauer technique

By Mössbauer absorption experiments the magnetic hyperfine splitting has been observed for the 2+ states of¹⁸⁰W and¹⁸²W in a tungsten iron alloy (3.6 at%W). Since theg-factor of the 2+ state of¹⁸²W is known the measured splitting of the¹⁸²W line could be used for the calibration of the magnetic hyperfine field and the measurement with¹⁸⁰W gave then for the unknowng ₂₊-factor of¹⁸⁰W: $$g_{2 + } (^{180} W) = 0.260 \pm 0.017.$$ By use of a WO₃ absorber the electric quadrupole splittings in the same states were measured. The ratio of the quadrupole moments was derived $$\frac{{Q_{2 + } (^{180} W)}}{{Q_{2 + } (^{182} W)}} = 0.983 \pm 0.022.$$ This ratio is somewhat smaller, but more accurate than the weighted means of previous results and in disagreement with the theoretical prediction. A similar measurement with¹⁷⁸Hf and¹⁸⁰Hf and a HfO₂ absorber gave $$\frac{{Q_{2 + } (^{178} Hf)}}{{Q_{2 + } (^{180} Hf)}} = 1.052 \pm 0.021.$$ This result is larger than the average of previous measurements and agrees with theory. The isomer shifts of the Mössbauer lines of¹⁸⁰W and¹⁸²W were measured for sources in a tantalum metal environment and for absorbers of metallic tungsten. Different signs were observed which indicate that the mean squared charge radius of the 2+ state of¹⁸²W is larger than that of the ground state whereas for¹⁸⁰W the ground state has the larger 〈r ²〉-value.     

Temperature dependence of the localized magnon mode in MnF2 : Co

The localized magnon mode in MnF₂ : Co was studied by far infrared resonance techniques. The halfwidth at 8 K is 1 cm^-1, about three times smaller than that obtained by other experimental methods. Therefore, accurate measurements of the temperature dependence are possible between 8 and 40 K. The temperature dependence of the effective g-factor is attributed to spin wave renormalization. The half width is magnetic field dependent at higher temperatures and can be approximated by a T² law.     

EPR and Optical Absorption Study of Cu2+-Doped Diammonium Hexaaqua Magnesium Sulphate Single Crystals

Electron paramagnetic resonance (EPR) study of Cu²⁺ ions doped in diammonium hexaaqua magnesium sulphate single crystal over the temperature range of 4.2–320 K is reported. Copper enters the lattice substitutionally and is trapped at two magnetically equivalent sites. The spin Hamiltonian parameters are evaluated at 320, 300, 77, and 4.2 K. The angular variations of the resonance lines in three mutually perpendicular planes ab, bc* and c*a are used to determine principal g and A values. The observed spectra are fitted to a spin Hamiltonian of rhombic symmetry with parameters of Cu²⁺ at 77 and 4.2 K: g _xx  = 2.089, g _yy  = 2.112, g _zz  = 2.437 (±0.002) and A _xx  = 38, A _yy  = 14, A _zz  = 110 (±2) × 10^?4 cm^?1. The ground state wave function of Cu²⁺ ion in this lattice is determined. The g-factor anisotropy is calculated and compared with the experimental value. The optical absorption spectra of the crystal are also recorded at room temperature. With the help of assigned bands the crystal-field parameters (Dq, Ds and Dt) are evaluated. By correlating the optical and EPR data, the nature of bonding in the complex is discussed. The temperature dependence of the g values is explained to conclude the occurrence of both static and dynamic Jahn–Teller effects over the temperature range of investigation.     

Nuclearg-factors of theJ π=21/2+isomer in112In and theJ π=6+ 112Sn

Theg-factor of theJ ^π=21/2⁺ isomeric state in¹¹¹In (T _1/2=13.3 ns) and of theJ ^π=6⁺ isomeric state in¹¹²Sn (T _1/2=13.7 ns) were measured using the spin rotation method. The result obtained for theJ ^π=21/2⁺ level in¹¹¹In,g=+0.47 (2), indicates that this state has an almost pure ((πg _9/2)^?1 νg _7/2 νd _5/2) shell model configuration. The experimental valueg=+0.04 (3) for theJ ^π=6⁺ isomer in¹¹²Sn agrees with the theoretical value calculated within the frame of the BCS model.     

Effect of Mo doping on magnetic and transport properties of La0.5Sr0.5CoO3

The substitutional effect of Mo on the magnetic and transport properties of double exchange ferromagnets, La_0.5Sr_0.5Co_1−x Mo_xO₃ (0?x?0.2) has been investigated. Substitution of 10% Mo at the Co-site of La_0.5Sr_0.5CoO₃ decreases the Curie temperature by ∼60 K than that of the parent compound and the long-range ferromagnetic ordering disappears for x?0.2. The Mo-doped samples, however, undergo a transition from the parent metallic state to the insulating state below T_c. The insulating state is found to obey Mott's variable range hopping of conduction. The effect of Mo substitution is attributed to the factors namely, (i) the dilution of magnetic Co sublattice, (ii) the reduction of Co⁴⁺/Co³⁺ ratio resulting in a reduced carrier concentration and (iii) disruption of the intermediate spin structure of Co, namely Co³⁺: t_2g⁵e_g¹.     

Near infrared magneto-absorption in the laser material KZn1−xCoxF3

Infrared absorption (1.4–2μm) of KZn_1−xCo_xF₃ (0⩽ x<0.15) at 4.2 K has been studied in a magnetic field (B⩽7 T). Large field-induced splittings were observed for Co²⁺-ion lines. Details of the cobalt concentration dependence of the absorptivity at B = 0 and at field are given along with the dependences on field direction and strength. Assignments are made of the observed Co²⁺ single-ion and pair transitions. The data has enabled the determination of the infrared (IR) transition g values.     

Theoretical calculations of the optical band positions and spin-Hamiltonian parameters for Cr ions in Y2Ti2O7 crystal

The optical band positions and spin-Hamiltonian parameters (g factors g_g_? and zero-field splitting D) for the trigonal Cr³⁺ centers in Y₂Ti₂O₇ crystal are calculated from the complete diagonalization (of energy matrix) method based on the two-spin-orbit-parameter model. In the calculations, the contributions to spectral data from both the spin-orbit parameter of central dⁿ ion and that of ligand ion are considered and the crystal field parameters used are estimated from the superposition model. The calculated results are in reasonable agreement with the experimental values. The defect structures of Cr³⁺ center is suggested.     

Magnetic moment of the 3+, one millisecond isomer in self-conjugate46V

Theg-factor of the one millisecond isomer (first excited state at 801 keV) in self-conjugate⁴⁶V was measured by the perturbed angular distribution method. The isomeric state was populated by the heavy ion reaction³²S(¹⁶O,pn)⁴⁶V and recoil implanted into a liquid metal. The result,g=+0.546(10) extends the known isoscalar moments to heavier nuclei and is in close agreement with all previously measured isoscalar moments in thef _7/2 shell. Theγ-ray angular distribution confirms the spin 3 assignment of the isomeric state.