Indirect measurements of the Jahn-Teller quenched spin-orbit splitting in the 5T2g-state of KMgF3:Fe2+

The energy separation of the first excited spin-orbit States Γ_3g, Γ_4g from the Γ_5g ground state, in the orbital ⁵T_2g triplet state of Fe²⁺ in KMgF₃, has been estimated from temperature dependence measurements on the 7860 cm^-1 zero-phonon-line (ZPL) transition from Γ_5g to the orbital ⁵E_g doublet state. Using a simplified crystal field energy level model, we find the Γ_5g Γ_3g, Γ_4g separation to be ～30 cm^-1, indicating that the vibronic Jahn-Teller coupling is considerably stronger in KMgF₃:Fe²⁺ than in MgO:Fe²⁺. Far infrared absorption data on KMgF₃:Fe²⁺ in magnetic fields up to 6T, are found to be consistent with this interpretation.     

Far infrared absorption of Fe2+ in KMgF3

Far infrared absorption in cubic KMgF₃ doped with Fe²⁺ is reported . A line is observed at 87cm^?1, which is assigned to the (Γ_5g → Γ_3g, Γ_4g) transition in the Fe²⁺. The reduction in the spin-orbit coupling from the free ion value has been predicted by Ham, Schwarz and O'Brien.     

Far-infrared absorption of MgO: Fe2+ in magnetic fields

We have measured the far-infrared absorption of iron-doped MgO in the wavenumber region 10–200 cm^?1 and in magnetic fields up to 6 T. Absorption peaks found at 107.0 and 110.5 cm^?1 are assigned to magnetic dipole transitions between the spin-orbit Г_5g groundstate (J = 1) and the Г_3g, Г_4g excited states (J = 2) of the Fe²⁺ -ion at a cubic site. The observed magnetic field dependence shows that Г_4g is the higher excited level, so that the crystal field order of the levels is not changed by the reduction of the spin-orbit splitting attributed to a dynamic Jahn-Teller effect. An additional absorption peak at 33.4 cm^?1 is found to split in magnetic field.In iron-doped KMgF₃ absorption peaks at 52 and 87 cm^?1 that have previously been attributed to the same transitions of Fe²⁺ are found to remain unshifted and unsplit in magnetic fields up to 6 T.     

Bilinear and biquadratic exchange interactions and their effect on magnetic susceptibilities of KMgF3: Mn and KZnF3: Mn

Exchange interaction constants of nearest (J₁) and next-nearest-neighbor (J₂) Mn²⁺ in KMgF₃: Mn and KZnF₃: Mn have been evaluated from the magnetic susceptibilities. For KZnF₃: Mn, J₁ = 8.2 ± 0.5 K; this is consistent with the ESR value if biquadratic exchange is present.     

Spectroscopic studies on Fe and Mn doped SrB4O7 glasses

EPR and optical absorption studies on Fe³⁺ and Mn²⁺ doped strontium tetraborate (SrB₄O₇) glasses are carried out at room temperature. The EPR spectrum of the Fe³⁺ doped glass consists of signals with g-values 9.04, 4.22 and 2.04, whereas the EPR spectrum of Mn²⁺ doped glass exhibits a characteristic hyperfine sextet around g=2.0. The spectroscopic analyses of the obtained results confirmed distorted octahedral site symmetry for the Fe³⁺ and Mn²⁺ impurity ions. Crystal field and Racah parameters evaluated from optical absorption spectra are: Dq=790, B=700 and C=3000 cm⁻¹ for Fe³⁺doped glass and Dq=880, B=700 and C=2975 cm⁻¹ for Mn²⁺ doped glass.     

ESR in X-irradiated As2O3 glass

X-irradiation of glassy As₂O₃ at 77K or 300K produces an unusually large density (～5×10¹⁸ cm^-3) of paramagnetic centers which are stable at 300K. The average spin-Hamiltonian parameters (g = 1.998, g_⊥ = 1.984, A₆ = 243G, A_⊥ = 114G) indicate that these centers are analogous to those previously observed in As₂Se₃ and As₂S₃ glasses and that they consist of unpaired electrons localized on a non-bonding 4p orbital of an As atom. Unlike the results obtained for As₂Se₃ and As₂S₃, the concommitant holes in As₂O₃ are trapped on Fe²⁺ impurity sites which become Fe³⁺ and not on non-bonding oxygen p orbitals. The radiation induced ESR is also accompanied by a stable optical absorption tail which lies within the band gap and increases exponentially with energy. This absorption can be partially bleached with the application of sub-band-gap light.     

Linear-chain ferromagnetism in the one-dimensional compounds CoCl2(pyrazole)2 and CoCl2(indazole)2

Two linear-chain compounds of formula CoCl₂L₂, with L = pyrazole (pz) and indazole (indz), have been investigated with the aid of IR, far-IR, ligand field and ESR spectra. Magnetic susceptibility data have been collected in the temperature region 4.2–80 K. Analysis of the susceptibility data in terms of the Ising model yielded the values of the ferromagnetic intrachain exchange constants J = 7.2(6) and 7.4(9) cm^-1 for the pz and indz compound, with corresponding g-values of g∥ = 7.9(7), g⊥ = 4.6(9) and g∥ = 10.8(9), g⊥ = 3(1), respectively. The results are discussed and compared with the similar compound CoCl₂(pyridine)₂. The influence of the bridge geometry and of the π-bonding properties of the organic ligands on the exchange constant are considered for the explanation of different J-values. It is suggested that the π-bonding properties of the organic ligand influence the magnitude of the superexchange constant to a great extent.     

New measurements of the emission spectra of Sm2+ in KMgF3 and NaMgF3 crystals

The fluorescence of divalent samarium in KMgF₃ and NaMgF₃ crystals is investigated. The emission is observed to originate from transitions between the ⁵D_J, and ⁷F_J multiplets of the 4?⁶ configuration. More precisely, the lowest ⁵D_J level, ⁵D₀, appears to be the most efficient emitting level in the temperature range 4–300K. Contrary to what has been reported elsewhere, the Sm²⁺ fluorescence in both crystals does not exhibit any broad band emission even at room temperature. The great number of lines in the ⁵D₀→⁷F_J patterns gives evidence of the multiple-center origin of the fluorescence.     

Near-infrared absorption of MgF2:Fe2+

The multiphonon sideband of the spin allowed transition 6T_2g:A₁ ? 2〉 → 6E_g:B₃ ? 2〉 within the 3d⁶ orbital of Fe²⁺ in D_2h symmetry was analyzed with respect to the one phonon absorption and density of states of the coupled phonon modes. Temperature dependence of the zero-phonon line shows, that the axial anisotropy of the S = 2 spin multiplet in the excited B₃ state is about 0.9 cm^-1.     

Decoupled magnetic subsystems in the random mixture FepCo1-p(C5H5NO)6(ClO4)2

Specific heat data on the random mixtures Fe_pCo_1-pL₆(ClO₄)₂, where L = C₅H₅NO, are presented. The Fe and Co magnetic atoms have competing anisotropies since the pure Fe and Co compounds are known to be good examples of the simple cubic, $\text{S =}\text{1}\text{2}$, Ising and XY magnet, respectively. The experimental data show the two magnetic subsystems in the mixtures to be almost completely decoupled, which is a consequence of the fact that the crystal field anisotropies of the Fe²⁺ and Co²⁺ ions, yielding g_∥ ? g_⊥ and g_⊥ ? g_∥, respectively, are very strong compared to the magnetic exchange interactions. Consequently the two magnetic subsystems experience one another as nonmagnetic impurities. A model is presented which explains these results, as well as those previously found for related random mixtures, in terms of two interpenetrating percolation clusters.     

Fourth-order spin Hamiltonian terms for Fe2+ in rutile structure antiferromagnet FeF2

The paper deals with the spectroscopic and magnetic properties of Fe²⁺ ions in FeF₂. The microscopic spin Hamiltonian theory for Fe²⁺ in crystalline environments with second-kind orthorhombic symmetry is considered. Explicit formulas for the parameters B₀⁽²⁾(D),B₂⁽²⁾(E), g_x, g_y, g_z and, for the first time in the literature, the fourth-order parameters B₀⁽⁴⁾, B₂⁽⁴⁾ and B₄⁽⁴⁾, are derived. Using semi-empirical data for the ⁵D-term energy levels of Fe²⁺ ion in FeF₂, the pressure dependence of the parameters B_q^(k) in the region from 0 to 133 kbar is discussed. The relative role of the fourth-order parameters with respect to the second-order ones is found to increase strongly with pressure (e.g. in the region studied, D increases only by a factor of 3, whereas B₀⁽⁴⁾ increases by a factor of nearly 20). The magnetocrystalline anisotropy of FeF₂; is considered in the strong anisotropy model taking into account the fourth-order spin Hamiltonian terms. The uniaxial anisotropy constants K₁ and K₂ are derived theoretically and their pressure dependence is discussed quantitatively. The theory and numerical results of this paper are useful with regard to Fe²⁺ in other isomorphic fluorides, namely: MgF₂, ZnF₂, VF₂ and MnF₂. It is found that the fourth-order spin Hamiltonian parameters are accessible to experimental detection from spectroscopic studies on Fe²⁺ in non-magnetic fluorides and magnetic studies on Fe²⁺ : MnF₂ and FeF₂, preferably under high pressure.     

α-Al2O3单晶中Fe3+离子的电子顺磁共振

本文对α-Al₂O₃单晶体中Fe³⁺离子在室温下,X波段进行了电子顺磁共振研究,发现Fe³⁺离子实际上占据四种磁性不等价晶位。在同一氧离子层间的两种晶位上的Fe³⁺离子具有相同的自旋哈密顿参量,而不同氧离子层间的晶位上的Fe³⁺离子具有不同的自旋哈密顿参量,两种自旋哈密顿参量为:(1)g_‖=2.001,g_⊥=2.003,D=1679 关键词：     

EPR study of Ce ions in lutetium silicate scintillators Lu2Si2O7 and Lu2SiO5

Two Ce³⁺-doped scintillator crystals, LSO (Lu₂SiO₅:Ce) and LPS (Lu₂Si₂O₇:Ce), are studied by EPR spectroscopy. The analysis indicates that Ce³⁺ substitutes for Lu³⁺ ion in a C₂-symmetry site for LPS and in two C₁-symmetry sites for LSO, with a preference for the largest one, with 6+1 oxygen neighbors. Angular dependence of the EPR spectrum shows that the electronic ground state of Ce³⁺ is different in these two matrices. It is mainly composed of |M_J|=5/2 state in LPS and |M_J|=3/2 state in LSO. The temperature dependence of the linewidth shows a noticeably long spin lattice relaxation time, especially in LPS, which is the result of a stronger crystal field in LPS than in LSO.     

EPR identification of the iron charge transfer in CuAlS2:Fe

The EPR spectrum of Fe²⁺ has been observed in CuAlS₂. It consists of a single line with g^eff₆ ≈ 9.5 at 34.8 GHz. An analysis yields the following crystal field parameters: 10Dq ≈ 3600 cm^?1, μ ≈ 800 cm^?1 and δ ≈ 900 cm^?1. It is found that Fe³⁺ can be converted into Fe²⁺ by irradiation with light of energies considerably less than the band gap. These results directly confirm the charge transfer model previously suggested for CuAlS₂:Fe.     

The pentad rotation-vibrational states of 12CD4: Wavenumber analysis of infrared and Raman spectra of the ν1, ν3, 2ν2, ν2 + ν4, and 2ν4 bands

The so-called pentad of ¹²CD₄ consists of the vibrational states v₁ = 1(symmetry A₁), v₃ = 1(F₂), v₂ = 2(A₁ + E), v₂ = v₄ = 1(F₁ + F₂), and v₄ = 2(A₁ + E + F₂). All states are located in the 1950 to 2250-cm^?1 region and all are strongly interacting. In the present work we have assigned more than 5000 infrared rotation-vibrational transitions and 163 isotropic Raman transitions from the vibrational ground state to the pentad. We have used infrared and Raman spectra of a resolution better than 0.01 cm^?1. From the experimental wavenumbers 2567 pentad rotation-vibrational energy levels with J ≦ 20 have been determined. These levels are reported in the paper. The levels have been used for refinements of the spectroscopic constants of two physically different effective Hamiltonians for the pentad states. For all levels with J ≦ 12 an unweighted standard deviation of 0.004 cm^?1 is obtained for both Hamiltonians, whereas the standard deviation increases more or less rapidly with J above 12 due to the imperfections of the Hamiltonians. The values of the spectroscopic constants of both Hamiltonians (85 and 106, respectively) are reported and the effects of the approximations are discussed.     

Light scattering by magnetic excitons in (FeMn)F2

The transitions between the low lying crystal field split states A_1g and B_1g of the Fe²⁺ ions in pure FeF₂ and in the mixed antiferromagnet Fe_1-xMn_xF₂ have been investigated with Raman light scattering. From the Raman polarization rules the lines have been identified as arising from the magnetic excitons associated with the transitions. The energy and the line-width of the strongest line are studied as a function of the concentration x. From the energy measurement we estimate that the single ion anisotropy parameter D of the Fe²⁺ ions varies from 6.46 cm^-1 in pure FeF₂ to 8.03 cm^-1 in MnF₂: Fe.     

Ce and Pr5d-energy levels in the (pseudo) perovskites KMgF3 and NaMgF3

The location of the 5d-energy levels of Ce³⁺ and Pr³⁺ in the cubic perovskite KMgF₃ and in the distorted perovskite NaMgF₃ was determined from spectroscopic studies in the vacuum ultraviolet. It is established that Ce³⁺ and Pr³⁺ ions both occupy the same site in each host: K⁺ sites for KMgF₃ and Na⁺ sites for NaMgF₃. The small crystal field splitting and the small value of the centroid shift of the 4fⁿ⁻¹5d-configuration yield a relatively high energy for the lowest 5d state of both Ce³⁺ and Pr³⁺. The lowest 5d state of Pr³⁺ in both hosts is found at energy higher than the 4f² state, enabling the photon cascade emission to occur.     

EPR and magnetic susceptibility studies of iron ions in ZnO-Fe2O3-SiO2-CaO-P2O5-Na2O glasses

Room temperature electron paramagnetic resonance (EPR) spectra and temperature dependent magnetic susceptibility data have been obtained on bulk x(ZnO,Fe₂O₃)(65−x)SiO₂20(CaO, P₂O₅)15Na₂O (6≤x≤21 mole%) glasses prepared by melt quenching method. EPR spectra of the glasses revealed absorptions centered at g≈2.1 and 4.3. The variations of the intensity and line width of these absorption lines with composition have been interpreted in terms of the variation in the concentration of the Fe²⁺ and Fe³⁺ ions in the glass and the interaction between the iron ions. EPR and magnetic susceptibility data of the glasses reveal that both Fe²⁺ and Fe³⁺ ions are present in the glasses, with their relative concentration being dependent on the glass composition. The studies reveal superexchange type interactions in these glasses, which are strongly dependent on their iron content.     

EPR parameters and local lattice structure study of V ions in CdCl2 and CsMgCl3 crystals

The local lattice structure and EPR parameters (D, g_‖, g_⊥) have been studied systematically on the basis of the complete energy matrix for a d³ configuration ion in a trigonal ligand field. By simulating the calculated optical and EPR spectra data to the experimental results, the local distortion parameters (ΔR, Δθ) are determined for V²⁺ ions in CdCl₂ and CsMgCl₃ crystals, respectively. The results show that the local lattice structure of CdCl₂:V²⁺ system exhibits a compression distortion (ΔR=−0.0868 Å) while that of CsMgCl₃:V²⁺ system exists an elongation distortion (ΔR=0.0165 Å). The different distortion may be ascribed to the fact that the radius of V²⁺ ion is smaller than that of Cd²⁺ ion or larger than that of Mg²⁺ ion. Moreover, the relationships between EPR parameter D and local structure parameters (R, θ) as well as the orbital reduction factor k and g‐factors (g_‖, g_⊥) are discussed.     

Infrared and Zeeman effect measurements of ferromagnetically coupled Nd ions in weakly doped LiYF4 crystals

Crystal-field infrared active excitations and photoluminescence of Nd³⁺ ions in weakly doped LiYF₄ have confirmed that the concentration dependent satellite lines accompanying the Nd³⁺ crystal-field optical transitions are due to four ferromagnetically coupled pairs of Nd³⁺ ions in undistorted Y³⁺ sites with the exchange energies J₁=0.9, J₂=1.6, J₃=3.1 and J₄=4.5 cm⁻¹, respectively. A linear Zeeman splitting of the Nd³⁺ ion ⁴F_3/2→⁴I_9/2 transition is observed and the g-factors (g_∥=0.2±0.1; g_⊥=0.97±0.01) associated with the ⁴F_3/2 lowest level are determined.