Deformation change in light iridium nuclei from laser spectroscopy

Laser spectroscopy measurements have been performed on neutron-deficient and stable Ir isotopes using the COMPLIS experimental setup installed at ISOLDE-CERN. The radioactive Ir atoms were obtained from successive decays of a mass-separated Hg beam deposited onto a carbon substrate after deceleration to 1kV and subsequently laser desorbed. A three-color, two-step resonant scheme was used to selectively ionize the desorbed Ir atoms. The hyperfine structure (HFS) and isotope shift (IS) of the first transition of the ionization path 5d ⁷6s ²⁴ F _9/2 → 5d ⁷6s6p ⁶ F _11/2 at 351.5nm were measured for ^182-189Ir, ¹⁸⁶Ir ^m and the stable ^{191, 193}Ir. The nuclear magnetic moments μ_I and the spectroscopic quadrupole moments Q_s were obtained from the HFS spectra and the change of the mean square charge radii from the IS measurements. The sign of μ_I was experimentally determined for the first time for the masses 182≤A≤189 and the isomeric state ¹⁸⁶Ir ^m . The spectroscopic quadrupole moments of ¹⁸²Ir and ¹⁸³Ir were measured also for the first time. A large mean square charge radius change between ¹⁸⁷Ir and ¹⁸⁶Ir ^g and between ¹⁸⁶Ir ^m and ¹⁸⁶Ir ^g was observed corresponding to a sudden increase in deformation: from β₂ ≃ + 0.16 for the heavier group A = 193, 191, 189, 187 and 186m to β₂≥ + 0.2 for the lighter group A = 186g, 185, 184, 183 and 182. These results were analyzed in the framework of a microscopic treatment of an axial rotor plus one or two quasiparticle(s). This sudden deformation change is associated with a change in the proton state that describes the odd-nuclei ground state or that participates in the coupling with the neutron in the odd-odd nuclei. This state is identified with the π3/2⁺[402] orbital for the heavier group and with the π1/2^-[541] orbital stemming from the 1h _9/2 spherical subshell for the lighter group. That last state seems to affect strongly the observed values of the nuclear moments.     

Theoretical study of the electron paramagnetic resonance parameters and local structure for the tetragonal Ir<Superscript>2+</Superscript> centre in NaCl

The electron paramagnetic resonance (EPR) parameters (the g factors, hyperfine structure constants and the superhyperfine parameters) for the tetragonal Ir²⁺ centre in NaCl are theoretically investigated from the perturbation formulas of these parameters for a 5d⁷ ion in tetragonally elongated octahedra. This impurity centre is attributed to the substitutional [IrCl₆]⁴⁻ cluster on host Na⁺ site, associated with the 4% relative elongation along the C ₄-axis due to the Jahn-Teller effect. Despite the ionicity of host NaCl, the [IrCl₆]⁴⁻ cluster still exhibits moderate covalency and then the ligand orbital and spin-orbit coupling contributions should be taken into account. In addition, the theoretical EPR parameters based on the Jahn-Teller elongation show good agreement with the observed values.     

EPR studies of Cu2+ and V4+ ions in phosphate glasses

Two lead-phosphate glass systems doped with both copper and vanadium ions in different ratios were studied by EPR (electron paramagnetic resonance) method. EPR spectra and parameters (g_‖ = 2.44, g_⊥ = 2.08 andA _‖ = 117.6 · 10⁻⁴ cm⁻¹) obtained for x(CuO · V₂O₅)(l−x)[2P₂O₅ · PbO] glasses withx ≤ 10 mol% suggest a tetrahedral (Td) coordination of Cu²⁺ ions and not a tetragonally elongated octahedron as has been assumed in previous works. The ground state of the paramagnetic electron is thed _xy copper orbital with a 4p_z contribution of 6%. For 20 ≤x ≤ 40 mol% a broad line (ΔB = 307 G) characteristic for clustered ions appears atg = 2.18. The V⁴⁺ ions are evidenced only in the spectra of x(CuO · 2V₂O₅)(1 −x)[2P₂O₅ · PbO] glasses and the resonance parameters suggest a pentacoordinated C_4v local symmetry for these ions. The hyperfine structures characteristic for Cu²⁺ and V⁴⁺ ions disappear for 10 ≤x ≤ 40 mol% due to the mixed exchange Cu²⁺−V⁴⁺ pair formation in these glasses.     

The infrared and laser Raman spectra of K2Zn(SO4)2 · 6H2O

The Raman spectra of the single crystal of K₂Zn(SO₄)₂·6H₂O belonging toC _2h ⁵ space group in the 40–1200 cm⁻¹ region in different scattering geometries and their spectra ofthe microcrystalline salt in the 1500-50 cm⁻¹ region have been reported. The dynamics of the crystal has been described in terms of 186 phonon modes under the unit cell approximation. The weak bands in the region 400–900 cm⁻¹ have been assigned to the libratory modes of H₂O molecules in contradiction to the assignments reported by Ananthanarayanan. The ambiguities existing in the literature about the assignments ofν ₂ ^c andν ₅ ^c modes of [Zn(H₂O)₆]²⁺ have also been removed. The translatory and libratory modes of different units of the crystal have been identified and assignments are made using farir and Raman data on various isomorphous tutton salts. It has been inferred that both SO ₄ ²⁻ tetrahedron and [Zn(H₂O)₆]²⁺ octahedron undergo linear as well as angular distortions from their free state symmetries in the crystal.     

An E.S.R. study of electron irradiated K3IrCl6 in a NaCl host lattice

Electron irradiation of the diamagnetic [Ir^IIICl₆]^3- ion in a NaCl host lattice produces two paramagnetic species. ESR studies indicate that these slightly different species can be assigned to a [Ir^IICl₆]^4- complex, with 5d ⁷ low spin configuration, arising from the capture of an electron in a d_z ² orbital. The almost zero value for the quadrupolar interaction and the negative value for the core polarization field per unpaired spin are discussed in terms of a ligand field theory and the group overlap integral for the A _1g molecular orbital is calculated from the experimental data.     

Influence of 50 MeV Lithium Ion Irradiation on Hyperfine Interactions of Cr0.5 Li0.5 Fe2O4

Spinel oxide Cr_0.5 Li_0.5 Fe₂O₄ has been irradiated at Nuclear Science Centre, New Delhi, by 50 MeV lithium ions of fluence 5*10¹³ ions/cm² and irradiation effect on hyperfine interactions has been investigated by Mossbauer spectroscopy. The Mossbauer spectrum of irradiated sample shows no paramagnetic doublet contribution and the hyperfine fields corresponding to the Fe³⁺ in the octahedral (B) and the tetrahedral (A) sites are very well separated. That is the observed superimposed A and B sites in unirradiated sample are split into separate lines after Li irradiation. Further an increase of the intensity of the lines (2)–(5) with respect to (1)–(6) signals an orientation of the hyperfine magnetic field towards a direction perpendicular to the ion path due to the irradiation induced strain by the latent tracks. The computer simulation of Mossbauer spectra indicated that the irradiated Fe³⁺-site occupancy of the A-site hyperfine field increased from 43% to 55% whereas the B-site hyperfine field decreased from 57% to 45% compared to unirradiated sample.     

Local Moment of Ir in Fe,Co and Ni Hosts Probed by Ir L 2,3 Edge X-Ray Magnetic Circular Dichroism

The formation of an induced 5d magnetic moment on Ir in Fe₉₇Ir₃, Co₉₅Ir₅ and Ni₉₅Ir₅ alloys has been investigated by X-ray magnetic circular dichroism (XMCD) and X-ray absorption spectra (XAS) measurements at Ir L _2,3 edges. Using a sum rule which relates the integrals of these spectra with the ground state expectation value of the orbital angular momentum 〈L _Z 〉 of the probed atom, the orbital moment m _orb of Ir could be determined as −0.071(2) μ _B in an Fe host, −0.067(2) μ _B in a Co host and −0.041(1) μ _B in a Ni host. The spin magnetic moment m _spin of Ir is also found to be the maximal in Fe and the minimal in Ni. The total moment of Ir is found to be approximately 1/5 of total moment of Fe, 2/13 of the total moment of Co, and 1/4 of the total moment of Ni. This revised version was published online in September 2006 with corrections to the Cover Date.     

Internal irradiation effects in239Pu doped K2Ca2(SO4)3): EPR,TSL and PAS investigations

The electron/hole trapped centres created during internal irradiation in²³⁹Pu doped K₂Ca₂(SO₄)₃ were investigated using electron paramagnetic resonance (EPR), thermally stimulated luminescence (TSL) and photoacoustic spectroscopic studies (PAS). These techniques were used to identify the defects and characterize the thermally induced relaxation processes. TSL studies of self (α)/γ-irradiated²³⁹Pu doped K₂Ca₂(SO₄)₃ revealed two glow peaks around 400 and 433K. Plutonium introduced as Pu⁴⁺ was partly reduced to Pu³⁺ due to self irradiation. This was ascertained from PAS studies. EPR studies carried out on these samples showed the formation of radical ions SO ₄ ⁻ , SO ₃ ⁻ , O ₃ ⁻ , etc. The thermal destruction of SO ₄ ⁻ ion was found to be associated with the prominent glow peak around 433K. Pu³⁺ was found to act as luminescent centre for the observed TSL glow. The trap depth for the glow peak at 433K has been determined from TSL and EPR data.     

Electron paramagnetic resonance studies in photorefractive crystals I: Hyperfine interaction and photoinduced charge transfer in233U5+ and238U5+ doped LiNbO3

Electron paramagnetic resonance studies were conducted on the photoinduced charge transfer and also hyperfine interaction of U⁵⁺ stabilized in photorefractive matrix LiNbO₃. This work deals with: (i) first observation of hyperfine structure due to²³³U (I=5/2) in its pentavalent state at octahedral sites and comparison with other possible site symmetries, (ii) photoinduced charge transfer as observable by EPR and its relevance to photorefractive behaviour of LiNbO₃. The effect of chemical bonding on the hyperfine interaction of 5f ¹ configuration was also studied by converting the existing literature data on²³⁵U⁵⁺ to that of²³³U⁵⁺ by standard methods. This suggests that progressive substitution of oxygen by F⁻, in the series UO ₆ ⁷⁻ , (UO₅F)⁶⁻ and (UO₄F₂)⁵⁻ drastically decreases the hyperfine coupling constantA _∥, along the local distortion axis. This trend is explained as being due to the absence of ligand ion along the distortion axis at U⁵⁺ site in trigonal LiNbO₃. The effects of illumination by copper vapor laser (CVL) on the intensity of the U⁵⁺ signal was studied in the 10–300K region. The kinetics of decay and restoration of U⁵⁺ was also studied between 10–100K range. The decay kinetics was found to obey double exponential. The reduction of concentration of U⁵⁺ with CVL-illumination and its restoration in the absence of light show that pentavalent uranium takes part in the photorefractive effects in LiNbO₃.     

Nuclear magnetic resonance on oriented192Ir in Fe and Ni

The hyperfine interaction of¹⁹²Ir nuclei as dilute impurities in Fe and Ni has been investigated with NMR on oriented nuclei. With the use of highly dilute and pure alloys the line widths could be reduced so far that the quadrupole splitting of¹⁹²IrFe and¹⁹²IrNi could be resolved. Taking hyperfine anomalies into account the ground state nuclear moments of¹⁹²Ir are deduced as |μ|=1.924(10)μ _N andQ=2.36(ll) b. The hyperfine field of IrNi was investigated as a function of the Ir concentrationc between 0.01 at % and 5 at %. The dependence ofH _HF onc was found to be significantly smaller than that reported from Mössbauer effect measurements. Forc=0.01 at %H _HF=?454.7(2.3)kG is deduced. The resonance shift with an external magnetic field has been studied precisely, yieldingK=0.012(23) andK=0.026(12) for the Knight-shift of¹⁹²Ir in Fe and Ni, respectively.     

Spin Hamiltonian parameters and local structures for tetragonal and orthorhombic Ir2+ centers in AgCl

The perturbation formulae of the spin Hamiltonian parameters (the anisotropic g factors, hyperfine structure constants and superhyperfine parameters) are established for a 5d⁷ ion in an orthorhombically elongated octahedron based on the cluster approach. These formulae are applied to the theoretical studies of the EPR spectra and the local structures for the tetragonal and orthorhombic Ir²⁺ centers in AgCl. For the tetragonal Ir²⁺ center, the uncompensated substitutional [IrCl₆]⁴ cluster is found to experience a relative elongation of about 0.08 Å along the C ₄ axis due to the Jahn–Teller effect. For the orthorhombic center, the ligand octahedron also suffers Jahn–Teller elongation (by about 0.08 Å) along the [001] (or Z) axis. Meanwhile, the ligand Cl intervening in the impurity Ir²⁺ and the next nearest neighbor silver vacancy V_Ag along the [100] (or X) axis may undergo an inward displacement of 0.004 Å towards the center of the octahedron due to electrostatic repulsion of the V_Ag. The calculated spin Hamiltonian parameters based on the above local structures show good agreement with experimental data for both centers.     

EPR of trivalent iron ions in a LiCaAlF6 crystal

The orientational dependences of the EPR spectra of Fe³⁺-doped LiCaAlF₆ single crystals (space group P31c, Z=2), grown at the Laboratory of Magnetic Radio Spectroscopy at Kazan’ State University, have been investigated in detail. The spectrum is described by a trigonal spin Hamiltonian with the following parameters: B ₂₀=40.072×10⁻⁴ cm⁻¹, B ₄₀=−5.799×10⁻⁴ cm⁻¹, B ₄₃=−4.281×10⁻⁴ cm⁻¹, A _s=24.33±1, A _p=6.13±1, g _∥=g _⊥=2.00217±0.0003. A theoretical calculation of the hyperfine structure parameters shows that they are described quite well when allowance is made for the overlapping of the wave functions of the paramagnetic center and the ligands (F⁻). Fiz. Tverd. Tela (St. Petersburg) 39, 488–490 (March 1997)     

Superhyperfine Structure of EPR Spectra in LiLuF<Subscript>4</Subscript>:U<Superscript>3+</Superscript> and LiYF<Subscript>4</Subscript>:Yb<Superscript>3+</Superscript> Single Crystals

Electron paramagnetic resonance (EPR) spectra of doped paramagnetic crystals LiLuF₄:U³⁺ and LiYF₄:Yb³⁺ have been investigated at a frequency of about 9.42 GHz in the temperature range of 10–20 K. The U³⁺ ion spectrum is characterized by g-factors g _∥ = 1.228 and g _⊥ = 2.516, and contains the hyperfine structure due to the ²³⁵U isotope with nuclear spin I = 7/2 and natural abundance of 0.71%. The observed hyperfine interaction constants are A _∥ = 81 G and A _⊥ = 83.8 G. Moreover, the spectrum reveals the well-resolved superhyperfine structure (SHFS) due to two groups of four fluorine ions forming the nearest surrounding of the U³⁺ ion. This SHFS contains up to nine components with the spacing between components being about 12.7 G. The SHFS is observed also in the EPR spectrum of the LiYF₄:Yb³⁺ crystal; up to 17 components with spacing of about 3.7 G may be traced. Some parameters of the effective Hamiltonian of the SHF interaction are estimated, the contribution of covalent bonding of f-electrons with ligands into these parameters is discussed. Authors' address: Igor N. Kurkin, Kazan State University, Kremlevskaya ulitsa 18, Kazan 420008, Russian Federation     

Quantum cutting in Gd<Subscript>2</Subscript>SiO<Subscript>5</Subscript>: Eu<Superscript>3+</Superscript> by VUV excitation

The emission and excitation spectra of Gd₂SiO₅∶Eu³⁺ were investigated using the VUV beam line of the Beijing Synchrotron Radiation Facility (BSRF). The experimental results were discussed in the frame of visible quantum cutting process involved in Gd³⁺−Eu³⁺ system. Upon direct excitation into the⁶G _J states of Gd³⁺, two visible photon emissions from Eu³⁺ were observed. Cursory evaluation proved that Gd₂SiO₅∶Eu³⁺ is an efficient visible quantum cutter.     

Deposition dynamics and chemical properties of size-selected Ir clusters on TiO2

We report a study of Ir_n/TiO₂ samples prepared by size and energy-selected deposition of Ir_n⁺ (n=1, 2, 5, 10, 15) on rutile TiO₂(1 1 0) at room temperatures. The Ir clusters are found to be formally in the zero oxidation state, and there are no significant shifts in Ir 4f binding energy with cluster size. Over a wide range of impact energies, both Ir XPS intensity and peak position are constant, indicating constant sticking coefficient, and no impact-driven redox chemistry. Low energy ion scattering spectroscopy (ISS) suggests that the deposited Ir clusters remain largely intact, neither fragmenting nor agglomerating, and retaining 3-D structures for the larger sizes. For impact energies above 10 eV/atom, comparison of ISS and XPS data show that the Ir clusters are penetrating into the TiO₂ surface, with the extent of penetration increasing with both per atom energy and cluster size. Temperature programmed desorption (TPD) of CO is used to further characterize the deposited Ir_n. This system shows pronounced substrate-mediated adsorption (SMA) in low CO exposures, with strong dependence on cluster size. ISS and sputtering experiments indicate that CO adsorbed via SMA is bound differently than CO adsorbed in high dose experiments. In experiments with sequential C¹⁶O and C¹⁸O doses, facile C¹⁶O → C¹⁸O exchange is observed for Ir₅ and larger clusters, but not for Ir₂. The peak CO desorption temperature is found to decrease with cluster size. The cycle of CO adsorption and heating comprising a TPD experiment have a dramatic effect on the sample morphology, leading to encapsulation of Ir by a thin TiO_x layer.     

Structural and magnetic properties of iron doped YBa2Cu3O6+y and of its impurity phases: A57Fe Mössbauer study

We study the properties of Fe-doped YBa₂Cu₃O_6+y , in connection with electric field gradient and hyperfine field calculations which we have performed for high spin Fe³⁺ and Fe⁴⁺ in the two copper sites, with various oxygen environments. We also briefly describe results obtained on Fe doped Y₂BaCuO₅ and on YBaCu FeO_5+δ.     

EPR and optical spectroscopy of impurities in two synthetic beryls

Two synthetic beryls (Al₂Be₃Si₆O₁₈) of different color (purple and blue-green) were studied with electron paramagnetic resonance (EPR) and optical spectroscopy. In both crystals, the known spectra of Cu²⁺ and Fe³⁺ were observed with the same relative intensity. In the purple sample heated at 700°C in hydrogen atmosphere, two different kinds of Mn²⁺ EPR spectra were observed. The main one is pseudoaxial, it arises from ions substituted for Al³⁺ at position 4c of the structure. The weaker one is more complex, it has orthorhombic symmetry and is characterized by an unusually large zero-field splitting (B ₂⁰ = 741 · 10⁻⁴ cm⁻¹) and an isotropic hyperfine constantA = 70 G. This spectrum arises from Mn²⁺ at position 6f in the structure, normally occupied by Be. From optics, the blue-green color arises from Cu²⁺, while the purple one is due to Mn³⁺.     

Electron spin resonance study of a CuIr2S4 single crystal

A spinel sulphide CuIr₂S₄ single crystal, which exhibits an orbitally induced Peierls phase transition at ～230?K, is investigated by electron spin resonance (ESR) spectroscopy. The phase transition is clearly manifested on the ESR spectra. It is suggested that the ESR signals are produced by a few non-dimerized Ir⁴⁺ ions. Moreover, an extra ESR spectrum appears at low temperature in addition to the paramagnetic ESR signals of Ir⁴⁺ ions, which is suggested to be caused by the Jahn–Teller effect of the non-dimerized Ir⁴⁺ ions. From the ESR results, it is found that the Jahn–Teller splitting energy ΔE _JT is much smaller than the spin-dimerization gap.     

NMRON studies of the antiferromagnetic and paramagnetic phases of54Mn-MnCl2 · 4H2O

Pulsed NMRON, CW NMRON and thermal NMR-NO methods have been utilized to study⁵⁴Mn-MnCl₂ · 4H₂O. The⁵⁴Mn spin-lattice relaxation timeT ₁ in zero applied field has been measured between 35 and 90 mK in the antiferromagnetic phase. Above 65 mK the dominant relaxation mechanism is a Raman process with the electronic magnons, but at lower temperatures a direct process takes over. NMRON has been observed for the first time in the paramagnetic phase, and a line width of 300 kHz, with both homogeneous and inhomogeneous contributions, is observed. In the antiferromagnetic phase the line width is 35 kHz, and there are also homogeneous and inhomogeneous contributions. The dependence ofT ₁ for the⁵⁴Mn spins on field and temperature was studied in the paramagnetic phase. AT ₁ minimum centred atB ₀=2.64 T was observed. The hyperfine parameter <⁵⁴ AS>/h=−513.6(3) MHz in the paramagnetic phase, and comparison with the value in the antiferromagnetic phase gives 0.013(1) for the zero point spin deviation.     

The thermal behaviour of the quadrupole hyperfine interaction in (NH4)2HfF6

A TDPAC investigation has been accomplished on (NH₄)₂ HfF₆ between 14 and 620 K. A phase transition was observed below 390 K. The low temperature phase is characterized by two non-equivalent sites for hafnium atoms in a 1∶1 ratio. The high temperature phase, on the other hand, is depicted by a unique quadrupole interaction. Above 400 K, the compound decomposes successively to NH₄ HfF₅, NH₄ Hf₂F₉ and HfF₄. An enthalpy of 76±4 kJ/mol could be determined for the (NH₄)₂ HfF₆→NH₄ HfF₅+NH₄F chemical reaction. The hyperfine interaction and thermal evolution of (NH₄)₂ HfF₆ was found to be quite similar to that of (NH₄)₂ ZrF₆.