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.     

Electric dipole transition cross sections and effective site symmetry of Eu3+ in pseudocentric K5Eu(MoO4)4

The fluorescence and absorption spectra of Eu³⁺ in K₅Eu(MoO₄)₄ have been measured at 300 K and 77 K. The fluorescence lifetime of the ⁵D₀ state is 1.4 ms at 300 K. The largest cross section $\text{σ(}{}^5\text{D}{}_0\text{→}{}^7\text{F}{}_2\text{(4)) = 1.3 × 10}{}^{\mathrm{?21}}\text{cm}{}^2$ and the removal of degeneracies require to replace the nearest neighbour D_3d symmetry of Eu³⁺ by the effective symmetries C₁, C₂ and C_s of the whole unit cell. It is shown that C₁ dominates because of the statistical distribution of K⁺ and Eu³⁺. The corresponding inhomogeneous broadening is observed at 77 K.     

Chemical diffusion in nonstoichiometric chromium sulfide,Cr2+yS3

Using the re-equilibration kinetic method the chemical diffusion coefficient in nonstoichiometric chromium sesquisulfide, Cr_2+yS₃, has been determined as a function of temperature (1073–1373 K) and sulphur vapour pressure (10?10⁴ Pa). It has been found that this coefficient is independent of sulphur pressure and can be described by the following empirical equation: $\text{D}\text{?}\text{Cr}{}_{\mathrm{2+y}}\text{S}{}_3\text{=50.86}\text{exp(-39070 cal/mole/}\text{RT)}\text{(cm}{}^2\text{s}{}^{\mathrm{?1)}}$. It has been shown that the mobility of the point defects inCr_2+yS₃ is independent of their concentration and that the self-diffusion coefficient of chromium in this sulfide has the following function of temperature and sulphur pressure: . (cm²s^?1).     

Laser time-resolved selective excitation of Nd3+ ions in KNdP4O12 crystals

The emission spectra of Nd³⁺ ions in KNd_xRE_1?xP₄O₁₂ (RE = Y, La and Pr) and KNd_xCr_1?xP₄O₁₂ crystals were investigated. Under selective excitation into ²G$\text{7}\text{2}$ + ⁴G$\text{5}\text{2}$ multiples at 1.6 K the fluorescence of Nd³⁺ ions in non-equivalent crystal sites was observed. The excitation spectrum of the ${}^4\text{F}\text{3}\text{2}$ fluorescence had a complex satellite structure. Time resolved measurements showed the dependence of the fluorescence decay on the excitation wavelength. Selective excitation into the satellite lines at the wings of the main transition led to strongly non-exponential decay. The low temperature results indicated that there is no spectral energy transfer between ions in different types of sites.     

Comparison of neutron diffraction and EPR results on the cubic crystal structures of piezoelectric Bi4Y3O12(Y = Ge,Si)

By means of neutron diffraction measurements the structure parameters of polycrystalline Bi₄Y₃O₁₂(Y = Ge, Si) crystallizing according to space group $\text{I}\text{4}\text{3d?T}{}^6{}_{\mathrm{d}}$ were determined at room temperature. With respect to the trigonal coordination of oxygen ions around Bi³⁺ the results are compared to EPR investigations on equivalent single-crystal specimens containing Gd³⁺ impurities on Bi sites. Corresponding approximations in the interpretation of the measurements are discussed. Although both methods yield similar systematic differences between the Ge- and Si-compounds, the influence of Gd on the structures appears to be substantial. Moreover point charge models should be improved with respect to details of the electron density distribution.     

Tunable room-temperature cw laser action in Cr3+: GdScAl-garnet

We report, for the first time, cw room temperature laser action of Cr³⁺:Gd₃Sc₂Al₃O₁₂. These crystals show a strong band fluorescence due to the ${}^4\text{T}{}_2\text{→}{}^4\text{A}{}_2$ transition with a lifetime of 150 μs. Laser pumping in the blue and red spectral range yields a minimum threshold of 170 mW and slope efficiencies up to 18.5%. The emission of the free running laser is centered at 784 nm with a FWHW of 5 nm. The extension of the Ga-garnets to Al-garnets as suitable host lattices for Cr³⁺ reveals the variety of garnet-structured crystals having an appropriate ligand field for continuously tunable laser operation.     

Absorption spectra of Ni2+ in (NH4)2Mg(SO4)2·6H2O and Co2+ in Na2Zn(SO4)2·4H2O

Optical absorption spectra of Ni²⁺ in (NH₄)₂Mg(SO₄)₂·6H₂O and Co²⁺ in Na₂Zn(SO₄)₂·4H₂O single crystals have been studied at room and liquid nitrogen temperatures. From the nature and position of the observed bands, a successful interpretation could be made assuming octahedral symmetry for both the ions in the crystals. The splitting observed for ${}^3\text{T}{}_{\mathrm{1g}}\text{(F)}$ band in Ni²⁺ and ${}^4\text{T}{}_{\mathrm{2g}}\text{(F)}$ band in Co²⁺ at liquid nitrogen temperature have been explained as due to spin-orbit interaction. The extra band observed at 16,325 cm^-1 in the case of Ni²⁺ at low temperature has been interpreted to be the superposition of vibrational mode of SO^2-₄ radical on ${}^3\text{T}{}_{\mathrm{1g}}\text{(F)}$ band. The observed band positions in both the crystals have been fitted with four parameters B, C, Dq and ζ.     

Spectral and temperature characteristics of Cs2Na(Er,Yb, Y)Cl6 upconverters

Spectral luminescence characteristics of the Cs₂Na(Er, Yb, Y)Cl₆ type upconverter have been measured in the range 300–650 K. A nearly sixfold decrease of the emission intensity of an upconverter was observed in the green area. This emission corresponds to two luminescence transition of Er³⁺ ions: ${}^2\text{H}{}_{\mathrm{<mtext>11</mtext><mtext>2</mtext>}}\text{→}{}^4\text{I}{}_{\mathrm{<mtext>15</mtext><mtext>2</mtext>}}$ and ${}^4\text{S}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}\text{→}{}^4\text{I}{}_{\mathrm{<mtext>15</mtext><mtext>2</mtext>}}$. A mechanism of the luminescence intensity decrease has been proposed, in which deexcitation of the ${}^4\text{S}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ level to the ${}^4\text{I}{}_{\mathrm{<mtext>13</mtext><mtext>2</mtext>}}$ level is caused by a neighbouring Er³⁺ ion being excited to the ${}^4\text{I}{}_{\mathrm{<mtext>9</mtext><mtext>2</mtext>}}$ level.     

Strengths and lorentz broadening coefficients for spectral lines in the ν3 and ν2 + ν4 bands of 12CH4 and 13CH4

Line strengths and self- and nitrogen-broadened half-widths were measured for spectral lines in the ν₃ and ν₂ + ν₄ bands of ¹²CH₄ and ¹³CH₄ from 2870–2883 cm^?1 using a tunable diode laser spectrometer. From measurements made over a temperature range from 215 to 297 K, on samples of ¹²CH₄ broadened with N₂, we deduced that the average temperature coefficients n, defined as $\text{b}{}_{\mathrm{<mtext>L</mtext>}}{}^0\text{(T) = b}{}_{\mathrm{<mtext>L</mtext>}}{}^0\text{(T}{}_0\text{)(}\text{T}\text{T}{}_0\text{)}{}^{\mathrm{?n}}$, of the Lorentz broadening coefficients for the ν₃ and ν₂ + ν₄ bands of ¹²CH₄ were 0.97 ± 0.03 and 0.89 ± 0.04, respectively. A smaller increase is observed in line half-width with increasing pressure for E-species lines, for both self- and nitrogen-broadening, than for other symmetry species lines over the range of pressures measured, 70 to 100 Torr.     

Satellite electron-diffraction in NbSe3 below T = 59 K

At temperatures below 59 K, coexistence of two types of satellite was observed in reciprocal lattice plane of b¹?c¹ as expressed by $\text{q}{}_1\text{= 0.24}\text{b}{}^1$ and $\text{q}{}_2\text{= 0.26}\text{b}{}^1\text{+0.50}\text{c}{}^1$. On the basis of nesting conditions by these q₁ and q₂, a feature of the Fermi surface for NbSe₃ is discussed.     

Etude d'un groupement (Ru3O12)13− en presence de degenerescence orbitale et de couplage spin-orbite

A trinuclear cluster (Ru₃O₁₂)^13? occurs in the Ba₄NbRu₃O₁₂, and Ba₄TaRu₃O₁₂ compounds where the oxydation states of ruthénium are +III and +IV. The exchange interaction between magnetic sites is described by a Hamiltonian, which takes account of the orbital degeneracy of the ${}^2\text{T}{}_{\mathrm{<mtext>2</mtext><mtext>g</mtext>}}\text{(}\text{Ru}{}^{\mathrm{3+}}\text{)}\text{and}{}^3\text{T}{}_{\mathrm{<mtext>1</mtext><mtext>g</mtext>}}\text{(}\text{Ru}{}^{\mathrm{4+}}\text{)}$ terms. For these ions, the spin-orbit coupling is the dominant effect and it appears that the low temperature magnetic susceptibility depends essentially on the orbital reduction factor and the distortion of the coordination octahedra. There is apparently no first order perturbation of the ground state due to the interaction between magnetic ions.     

The mechanism of 5D3−5D4 cross-relaxation in Y3Al5O12: Tb3+

The ${}^5\text{D}{}_3\text{?}{}^5\text{D}{}_3$ cross-relaxation of YAG:Tb³⁺ has investigated by analysis of the ⁵D₃ decay curve as a function of Tb³⁺ concentration. This technique is a more sensitive test of the mechanism than relative intensity measurements alone. It is shown that the relaxation is predominantly dipole-dipole in character (R₀ ～ 1.3nm), and insensitive to temperature. The population of the ⁵D₄ state following high energy excitation occurs almost entirely via cross-relaxation from the ⁵D₃ state.     

Jahn-Teller analysis of the 3T1(P) absorption band of Ni2+ in GaP

Comparison between experimental absorption due to the ${}^3\text{T}{}_1\text{(F)?}{}^3\text{T}{}_1\text{(P)}$ transition of substitutional Ni²⁺(d⁸) in GaP and theoretical predictions based on the Jahn-Teller model is presented. Numerical solution of the Hamiltonian, in which spin-orbit interaction and T₂-mode Jahn-Teller coupling are included, is in very good agreement with the energy position and intensities of the observed absorption lines.     

Chemiluminescence of IF in the gas phase reaction of I2 with F2

Emission from both the state and the previously unreported $\text{A}{}^3\text{Π}{}_1$ state of IF has been observed in the gas phase reaction of I₂ with F₂ at low pressures. For the state the transition moment and vibrational populations were extracted from the spectra by a least-squares method whereby theoretical band shapes were fit to the experimental data. The effect of flow rates of reactants and Ar on the relative emission from the two electronic states, the effect of pressure on the state, and extinction of emission near 470 nm all favor the population of excited electronic states through a four-center reaction complex, rather than association of F and I atoms.It is argued that there is an avoided curve crossing between the lowest two ³Π_0⁺ states of IF, and that the ground state dissociation energy is 23 229 ± 100 cm^?1. The radiative lifetime of the state is estimated to be 10^?3 sec and to be much shorter than that of the $\text{A}{}^3\text{Π}{}_1$ state.     

A study of valency changes of vanadium ions in Al2O3 by γ irradiation

The effect of γ irradiation at 300 K on the concentrations of vanadium ions V³⁺, V⁴⁺ and V²⁺ in Al₂O₃ has been studied quantitatively, using three techniques: optical absorption (V³⁺), low temperature thermal conductivity measurements (V⁴⁺) and EPR (V²⁺). Several single crystals of Al₂O₃ doped with vanadium in a large range of concentration $\text{(2.8 × 10}{}^{18}\text{? 1.3 × 10}{}^{20}\text{at.}\text{cm}{}^3\text{)}$ have been measured. The evolution of the respective concentrations by γ irradiation as a function of the total vanadium content C is quite different in the two regions $\text{C< 1.2 × 10}{}^{19}\text{at.}\text{cm}{}^3$ and C larger than this value. A consistent analysis of the results has nevertheless been achieved, leading to the determination of the absolute concentrations of the three ions in the as-received and γ irradiated states for all samples with $\text{C<4.2 × 10}{}^{19}\text{at.}\text{cm}{}^3$ (room temperature annealing is observed above this value). The concentrations of V⁴⁺ and V²⁺ ions are always small, but V⁴⁺ ions are more stable: they are present in the as-received state at a level of 1% of the total concentration and a maximum value of $\text{/}\text{?}\text{2.3 × 10}{}^{18}\text{at.}\text{cm}{}^3$ is observed in the γ irradiated state; on the other hand there are less than 4.7 × 10¹⁵V²⁺ ions per cm³ in the as-received state and the maximum value is only $\text{4.2 × 10}{}^{17}\text{at.}\text{cm}{}^3$. Charge transfer between V ions only is not sufficient to explain the experimental results and other defects must be involved in the γ irradiation effect.     

A study of the K = 3nA1 - A2 centrifugal splitting in the 3ν2 and 4ν2 states of PH3 using a difference-frequency laser system

A frequency tunable infrared source has been constructed by using the (Ar-laser) - (dyelaser) difference frequency method developed by Pine and applied to the observation of the overtone bands of PH₃ 3ν₂ ← 0 and 4ν₂ ← ν₂ in the 3.4 μm region and 4ν₂ ← 0 in the 1.6-μm region. A Stark modulation method was used to increase the sensitivity of detection. For transitions which were well modulated, the minimum detectable absorption coefficient was estimated to be ～3 × 10^?7 cm^?1 using a 3-m cell. Emphasis was placed on the observation of the A₁-A₂ splitting for K = 3n rotational levels. For the 3ν₂ state splittings were observed for K = 3, 6, and 9 because PH₃ is a very nearly spherical top in this state. The magnitude and the J dependence of the observed K = 3n splittings have been analyzed by using a normal symmetric rotor Hamiltonian and a centrifugal distortion term of the form $\text{τ}{}_{\mathrm{xxxz}}\text{[(J}{}_{\mathrm{+}}{}^3\text{+ J}{}_{\mathrm{?}}{}^3\text{)J}{}_{\mathrm{z}}\text{+ J}{}_{\mathrm{z}}\text{(J}{}_{\mathrm{+}}{}^3\text{+ J}{}_{\mathrm{?}}{}^3\text{)]}\text{4}$.     

Electron exchange between Fe2+ and Fe3+ ions on octahedral sites in spinels studied by means of paramagnetic Mössbauer spectra and susceptibility measurements

Mössbauer spectra were obtained of the paramagnetic spinels $\text{Zn}{}^{\mathrm{2+}}\text{|}\text{Zn}{}^{\mathrm{2+}}{}_{\mathrm{<mtext>(1?x)</mtext><mtext>2</mtext>}}\text{Ti}{}^{\mathrm{4+}}{}_{\mathrm{<mtext>(1+x)</mtext><mtext>2</mtext>}}\text{Fe}{}^{\mathrm{3+}}{}_{\mathrm{<mtext>(1?</mtext><mtext>x)</mtext>}}\text{Fe}{}^{\mathrm{2+}}{}_{\mathrm{x}}\text{|}\text{O}{}_4$ and susceptibilities were measured. The strong difference between the paramagnetic Fe²⁺ and Fe³⁺ spectrum, due to the different quadrupole splitting, is used for the distinction between the two species. At 300 K a superposition of the Fe³⁺ and the Fe²⁺ spectra is found for most of the iron and, in addition, some continuous absorption. The latter is strongest for equal Fe³⁺ and Fe²⁺ concentration $\text{(x =}\text{1}\text{2}\text{)}$ while it disappears towards the end members (Fe³⁺ only or Fe²⁺ only) as well as with decreasing temperature (between 78 and 200 K). From this it is concluded that it arises from thermally activated electron exchange, the frequency of which passes a “critical” value of ～10⁸ sec^?1 for increasing temperature. Paramagnetic susceptibilities are found to obey a Curie-Weiss law down to low temperatures. From the dependence of the asymptotic Curie temperature on the composition the magnetic interaction parameters J₁₁ = ?1.4 K, J₂₂ = ?3.3 K and J₁₂ = + 1.6 K for the Fe³⁺Fe³⁺, Fe²⁺Fe²⁺ and Fe³⁺Fe²⁺ interactions are derived. The experimental results are discussed in terms of a hopping model with an activation energy q ～- 0.12eV and a non-equivalence of the octahedral sites expressed by a varying potential energy difference U₀ between neighbouring sites. The continuous absorption at 300 K for $\text{x =}\text{1}\text{2}$ is attributed to about 17% of the iron on sites with U₀ running from 0 to ??0.06 eV. The ferromagnetic Fe³⁺, Fe²⁺ interaction (J₁₂) is attributed to electron transfer from localized Fe²⁺ ions to Fe³⁺ neighbours via a transfer integral b of the order of 0.05 eV. The magnitudes of J₁₂ and b are tentatively explained.     

Low temperature specific heats of nearly one-dimensional antiferromagnet: CuCl2·2NC5H5

Transition temperature to LRO state was found at T_N=1.14K for nearly one-dimensional antiferromagnet CuCl₂ · 2NC₅H₅. Intra- and inter-chain exchange constants J and J′ were estimated, $\text{kT}{}_{\mathrm{<mtext>N</mtext>}}\text{J}\text{=0.082}$ and $\text{J′}\text{J}\text{=3×10}{}^{\mathrm{?3}}$, respectively. Comparison with those of TMMC implies highly one-dimensional character.     

Kerr-effect and dielectric tensor elements of magnetite (Fe3O4) between 0.5 and 4.3 eV

The complex polar Kerr effect (rotation and ellipticity) of magnetite single crystals has been measured at room temperature between 0.5 and 4.3 eV. From the magneto-optical data and the optical constants, the off-diagonal elements (?_xy) of the dielectric tensor has been derived. Three well separated magneto-optical transitions have been indentified. At about 0.75 eV one strong magneto-optical structure with a diamagnetic line shape is assigned to a $\text{3d}{}^6\text{→3d}{}^5\text{(}{}^6\text{A}{}_{\mathrm{1g}}\text{) 4s}$ transition from Fe²⁺ in octahedral sites. Two other structures with paramagnetic line shapes near 1.85 and 2.90 eV are assigned to the orbital promotion processes $\text{3d}{}^6\text{(Fe}{}^{\mathrm{2+}}{}_{\mathrm{oct}}\text{)→3d}{}^5\text{(}{}^4\text{T}{}_{\mathrm{1g}}\text{) 4s}$ and $\text{3d}{}^5\text{(Fe}{}^{\mathrm{3+}}{}_{\mathrm{tet}}\text{)→3d}{}^4\text{(}{}^5\text{T}{}_2\text{) 4s}$, respectively, which take into account Fe 3d^n?1 final state effects.     

ESR and superconductivity of Nd3+ and Gd3+ in ZrIr2

We report low temperatures ESR and Superconductivity experiments on Nd³⁺ and Gd³⁺ in the superconducting cubic intermetallic compound ZrIr₂. The ratio of the squares of the effective 4f-conduction electron exchange parameters corresponding to Nd³⁺ and Gd³⁺ ($\text{J}{}^2{}_{\mathrm{s-Nd}}\text{J}{}^2{}_{\mathrm{s-Gd}}$) were extracted both from the thermal broadening of the ESR linewidths and from the initial depression of the superconducting critical temperature, and were found to be comparable. Nd³⁺ was found to have a larger exchange parameter than of Gd³⁺.