ESR of Fe3+ -Rhombic,Fe2+ -Vo and Fe1+ -Vo complexes in SrTiO3

Three new Fe-defect complexes have been identified by ESR in Fe doped crystals of SrTiO₃. These are an Fe³⁺ center with rhombic fine structure in the “as-grown” crystals, and the vacancy associated complexes Fe²⁺ -V_o and Fe¹⁺ -V_o in “reduced” crystals. Photo-excited charge transfer effects are observed for these centers.     

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.     

Identification of Fe4+ and Fe5+ charge-transfer photochromic absorption bands in SrTiO3

Optical absorption and the enhancement and bleaching of Fe³⁺ and Fe⁵⁺ electron paramagnetic resonance in SrTiO₃: Al measured as a function of wavelength and time show that the photochromic absorption bands are due to electron transfer from O^2- valence states to Fe⁴⁺ and Fe⁵⁺. They occur at 2.09 and 2.82 eV for Fe⁴⁺ and at 1.99 and 2.53 eV for Fe⁵⁺.     

Evidence of equal Jahn-Teller coupling to Eg and T2g modes in KMgF3:Fe2+ from far infrared studies

From a study of the dependence of the far infrared (f.i.r.) spectra of KMgF₃:Fe²⁺ on impurity concentration and temperature, we identify them as due to magnetic dipole transition between the J = 1 and J = 2 states of Fe²⁺ and a resonant mode. The novelty of the work lies in demonstrating that in KMgF₃:Fe²⁺ the electronic orbital triplet is equally coupled to the E_g and T_2g modes of vibration and consequently vibronic interactions maintain the J-degeneracies.     

Thermal conductivity of KMgF3 : Cr2+

Observations of resonant scattering of thermal phonons Cr²⁺ ions in KMgF₃ are presented. The results are interpreted with the cluster model of Fletcher and Stevens.     

Ni2+ emission in MgO,KMgF3, KZnF3 and MgF2

The emission of Ni²⁺ ions in MgO, KMgF₃, KZnF₃ and MgF₂ crystals has been investigated. The fine structure on the bands at about 20 000 cm^-1 and 13 000 cm^-1 has been studied in detail and from this and the excitation spectra these bands are assigned to ${}^1\text{T}{}_{\mathrm{2g}}\text{→}{}^3\text{A}{}_{\mathrm{2g}}$ and ${}^1\text{T}{}_{\mathrm{2g}}\text{→}{}^3\text{T}{}_{\mathrm{2g}}$ transitions respectively.     

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.     

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.     

Stabilization of Fe2+ centers in LiNbO3: Ti waveguides

Holographic measurements in LiNbO₃: Ti waveguides are reported indicating a mode dependent enhancement of photoconductivity. This enhancement can be explained by a stabilization of Fe²⁺ centers in the waveguide which are responsible for optical damage effects.     

KMgF3:Cr3+的EPR参量和K+空位研究

EPR和ENDOR表明:顺磁离子取代KMgF₃中的Mg²⁺离子后,所处的环境具有轴对称。本文研究了KMgF₃:Cr³⁺的Δg=g_∥-g_⊥和零场分裂值D,证实KMgF₃:Cr³⁺中K⁺空位的存在。并且指出:由于K⁺空位,使Cr³⁺的最近邻F^-离子分 关键词：     

Electron paramagnetic resonance of Fe3+ in orthorhombic KNbO3

EPR spectra of KNbO₃:Fe single crystals are obtained in the - 10–110°C temperature range. The angular dependence of resonant lines is well reproduced by spin Hamiltonian parameters relevant to a Fe³⁺ impurity ion substituted to Nb ion in KNbO₃ crystal. The temperature behaviour of resonant lines is explained by a quadratic dependence of axial parameter D vs polarization P_s of the form D = βP²_s in the orthorhombic phase.     

Estimation of 4s covalent bonding of Fe2+ and Fe3+ ions in NiO

The charge densities of the 4s electrons in Fe²⁺ and Fe³⁺ ions in the ionic compound, NiO, were measured from an internal conversion experiment and compared with some predicted values on the basis of different theoretical methods.     

ESR-analysis of the chalcopyrite structure: CuGaS2:Fe3+

The electron spin resonance spectrum of Fe³⁺ impurity ions in the ternary semiconductor CuGaS₂ has been analysed. The two magnetically inequivalent metal sites in the chalcopyrite lattice could be distinguished via fourth order terms in the spin Hamiltonian. No serious deviations from stoichiometry could be detected in transport-grown crystals. It was found that traces of iron impurities lead to strong absorption in the visible and near infrared spectral region.     

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.     

Effects of Eu3+  Fe3+ exchange interaction on the spin Hamiltonian parameters of Fe3+ in EuGaG

The anisotropic exchange $\text{1}\text{3}\text{a}{}_{\mathrm{\mu \nu }}\text{Y}{}_{\mathrm{\mu \nu }}\text{(L}{}_{\mathrm{<mtext>Eu</mtext>}}\text{)S}{}_{\mathrm{<mtext>Eu</mtext>}}\text{· S}{}_{\mathrm{<mtext>Fe</mtext>}}\text{(0 < μ ? 6)}$ is incorporated with the isotropic exchange ?2 a₀₀S_Eu · S_Fe to interpret the observed spin-Hamiltonian parameters g and D of Fe³⁺ doped into EuGaG. Calculations from the observed g shifts yield a value of a₀₀ equal to 0.01 K. In order to explain the observed D shift, it is concluded that the spherical harmonics Y_μν(L_Eu) with μ > 2 are of dominant importance.     

Mössbauer spectra of Fe3+ and Fe2+ ions in hexagonal ferrite with w-structure

The hexagonal ferrite Fe₂W = BaFe₂²⁺Fe³⁺₁₆O₂₇ exhibits a sharp ⁵⁷Fe Mössbauer spectrum at 300 and 78 K. All seven sublattices in this complicated crystal structure are detected. Fast electron exchange between Fe²⁺ and Fe³⁺ ions gives rise to sharp lines and makes them indistinguishable. At 5 K the exchange is slow and the Fe²⁺ ions are detected from the presence of a weak subspectrum with broadened lines separated from the main spectrum of the Fe³⁺ ions. Analysis shows that the Fe²⁺ ions reside exclusively on one of the seven sublattices, which is occupied statistically by Fe²⁺ and Fe³⁺ ions in the ratio of 2 : 1. For SrFe²⁺₂Fe³⁺₁₆O₂₇ the situation is the same.     

ESR study of Fe3+ and Mn2+ ions on trigonal sites in ilmenite structure MgTiO3

Electron spin resonance has been observed for Fe³⁺ and Mn²⁺ ions occupying sites with trigonal symmetry in undoped and doped Verneuil-grown crystals of the ilmenite type compound MgTiO₃. At 300 K, the fine structure parameters in the spin Hamiltonian are (in 10^?4cm^?1) D = +844 (± 1), (a? F) = +118 (± 1), a = 69 (± 7) for Fe³⁺ and D = +164 (± 1), (a ? F) = +10.2 (± l), a = 7.0 (± 1) for Mn²⁺. These values are compared with literature data for Fe³⁺ and Mn²⁺ in other oxides, especially Al₂o₃, with particular reference to the recent “superposition” theory of the effect of a trigonal distortion. From the orientation of the axes of cubic pseudosymmetry of the spin Hamiltonian, and with the assumption that a has the same sign for both ions, it is proposed that Fe³⁺ and Mn²⁺ occupy the same octahedral site, namely the Mg²⁺ site. Anomalous line splittings observed for one sample were attributed to twinning on (0001) or {1120} planes.     

Excited-state absorption of Co2+ in MgF2 and KZnF3

We report on measurements of excited-state absorption spectra and absolute cross-sections in Co²⁺-doped KZnF₃ and MgF₂ at room temperature in the near-infrared domain. The data are compared with the predictions of the single-configuration co-ordinate model.     

Absorption spectra of Bi3+ and Fe3+ in Y3Ga5O12

The absorption spectra of Y₃Ga₅O₁₂:(Fe³⁺), Y₃Ga₅O₁₂:(Bi³⁺) and Y₃Ga₅O₁₂:(Bi³⁺, Fe³⁺) are presented to 40,000 cm^-1. Assignments are discussed and the transitions analysed in terms of their involvement in the large Faraday rotation observed in bismuth substituted iron garnets.     

Electron paramagnetic resonance of Fe3+ in KNbO3 at 300 K

In the orthorhombic phase of KnbO₃ an EPR spectrum of Fe³⁺ substitutional for Nb⁵⁺ has been observed with the main axis parallel to the pseudocubic one of the orthorhombic phase. The cubic parameter a is very close to the one in BaTiO₃. A second spectrum probably due to local charge compensation is also reported.