Spectral signatures of hyperfine and isotopic effects and of Tm-Tm pairs in LiYF4:Tm

We report on the high-resolution optical Fourier-transform spectroscopy of the LiYF₄:Tm³⁺ crystals. Splitting of several lines in the optical low-temperature polarized spectra was observed. We show that these splittings are caused by (i) the hyperfine interaction, (ii) the isotopic disorder in the lithium sublattice, and (iii) the interionic interaction between neighboring Tm ions. It is the first observation of the hyperfine splitting in the spectra of the Tm³⁺ ions in crystals. From the experimentally measured hyperfine splitting we evaluate the magnetic field at the thulium nucleus and calculate the magnetic g-factors of the excited crystal-field levels.     

High resolution measurements of the hyperfine structure of atomic Lanthanum for energetically low lying levels of odd parity

Doppler-reduced saturation absorption spectroscopy is applied to study the hyperfine structure of excited levels of Lanthanum. 16 transitions in the near infrared wavelength range are investigated. Precise values for the magnetic dipole hyperfine structure constants A as well as for the electric quadrupole hyperfine structure constants B of the isotope ¹³⁹La are determined for 14 levels of odd parity and nine levels of even parity. For levels of even parity a good agreement is found with values from previous measurements using sub-Doppler methods. For levels of odd parity previously determined values are improved and for two levels new values of the hyperfine structure constants are reported.     

Nuclear size correction to the hyperfine splitting in low- hydrogen-like atoms

The finite nuclear size effect on the hyperfine splitting of low-Z hydrogen-like atoms is studied in the external field approximation. A simple non-relativistic formula is proposed which expresses the nuclear size correction to the hyperfine splitting in terms of moments of the nuclear charge and magnetization distribution. The numerical results obtained via this formula are compared with corresponding results derived by means of the Zemach formula. A relativistic formula for the nuclear size correction to the hyperfine splitting is also derived. Received 18 March 2002 / Received in final form 14 November 2002 Published online 28 January 2003 RID="a" ID="a"e-mail: plunien@physik.tu-dresden.de     

Self-energy correction to the hyperfine splitting of the 1 s and 2 s states in hydrogenlike ions

The one-loop self-energy correction to the hyperfine splitting of the 1 s and 2 s states of hydrogenlike ions is calculated for both point and finite nuclei. The results of the calculation are combined with other corrections to find the ground state hyperfine splitting in lithiumlike ²⁰⁹Bi⁸⁰⁺ and ¹⁶⁵Ho⁶⁴⁺. Pis’ma Zh. éksp. Teor. Fiz. 66, No. 1, 19–22 (10 July 1997) Published in English in the original Russian journal. Edited by Steve Torstveit.     

EPR of Er3+, Nd3+, and Ce3+ ions in YAlO3 single crystals

EPR spectra of the Er³⁺, Nd³⁺, and Ce³⁺ ions substituting for the Y³⁺ ion in the YAlO₃ yttrium orthoaluminate lattice are studied. The EPR spectra of these rare-earth ions are described by a spin Hamiltonian of rhombic symmetry with an effective spin S=1/2. The principal values of the g tensors were determined from an analysis of the angular dependences of the EPR spectra. The orientation of the local magnetic axes of paramagnetic centers relative to the YAlO₃ crystallographic directions are shown to depend on the actual rare-earth species. The EPR spectra exhibit a hyperfine structure due to the ¹⁶⁷Er, ¹⁴³Nd, and ¹⁴⁵Nd odd isotopes, which permitted unambiguous identification of these spectra. The hyperfine coupling constants for the odd erbium and neodymium isotopes are determined.     

Mössbauer study of cobalt ferrite nanocrystals substituted with rare-earth Y ions

Mössbauer spectroscopy is used to characterize the crystallite size and structure of CoFe_2−xY_xO₄ (x=0, 0.1, 0.3, 0.5) ferrite nanocrystallites synthesized by the sol-gel auto-combustion method. The effect of the substitution of Fe³⁺ ions by Y³⁺ ions on the structure of cobalt ferrite nanocrystallites is investigated. The Mössbauer spectra showed two sets of six-line hyperfine patterns for all the samples, indicating the presence of Fe in both A and B-sites. On increasing the concentration of doped Y, the hyperfine field strength and the isomer shift first increase and then decrease, whereas the quadrupole splitting continuously increases. The superparamagnetism was observed for all the samples and the change of ratio of the superparamagnetism component reflects the size of crystal grain.     

Electron paramagnetic resonance and thermoluminescence study of Ag ions in Li2B4O7 crystals

Electron paramagnetic resonance (EPR) is used to investigate the effects of ionizing radiation on Ag-doped lithium tetraborate (Li₂B₄O₇) crystals. Two similar, yet distinct, trapped-hole centers (Ag²⁺ ions substituting for Li⁺ ions) are produced by 60 kV x rays. One Ag²⁺ ion, labeled Center A, has no nearby defects and the other Ag²⁺ ion, labeled Center B, has a neighboring impurity which is most likely a Ag⁺ ion substituting for a Li⁺ ion. The production and thermal decay properties of the two Ag²⁺ ions are described and their g matrices and ¹⁰⁷Ag and ¹⁰⁹Ag hyperfine matrices are obtained from the EPR angular dependences. The principal values of the g matrices are similar for the two centers, but the hyperfine principal values differ significantly (Center B has smaller values than Center A). There are also differences in the directions of the principal axes for the two centers. Together, these results imply (1) that the unpaired spin is less localized for Center B and (2) that the ground-state positions of the neighboring oxygen ions are different for Centers A and B. This explains why the peaks of the Ag²⁺ charge-transfer photoluminescence bands associated with Centers A and B occur at different wavelengths (502 and 725 nm, respectively). An isochronal pulsed thermal anneal shows that these radiation-induced Ag²⁺ ions serve as the recombination site for the intense thermoluminescence peak observed near 152 °C.     

Hyperfine splitting and isotope shift in the optical transition of Eu isotopes and electromagnetic moments of Eu

The laser-induced resonance fluorescence in an atomic beam was used in order to measure the hyperfine splitting of the 4f ⁷ 6s ² and 4f^{7 6s6p} levels in ^151,153,155Eu isotopes. The hfs constants A and B of the unstable ¹⁵⁵Eu were determined for the first time: MHz, MHz and MHz. With these data and after corrections for second-order hyperfine structure perturbations the nuclear moments of ¹⁵⁵Eu were deduced: n.m. and b. In addition new and more precise values of the hfs constants of the excited state for the stable ^151,153Eu were obtained. They are as follows: MHz, MHz and MHz, MHz. The hyperfine anomalies % and % were extracted from the corrected hfs constants. Received 28 July 1999 and Received in final form 14 January 2000     

Mössbauer study of Na0.82Co0.99Fe0.01O2

We studied by Mössbauer spectroscopy the Na_0.82CoO₂ compound using 1% ⁵⁷Fe as a local probe which substitutes for the Co ions. Mössbauer spectra at T=300 K revealed two sites which correspond to Fe³⁺ and Fe⁴⁺. The existence of two distinct values of the quadrupole splitting instead of a continuous distribution should be related with the charge ordering of Co⁺³, Co⁺⁴ ions and ion ordering of Na(1) and Na(2). Below T=10 K part of the spectrum area, corresponding to Fe⁴⁺ and all of Fe³⁺, displays broad magnetically split spectra arising either from short-range magnetic correlations or from slow electronic spin relaxation.     

Transferred hyperfine field of Rb2CoCl4 single crystals in the ferroelectric-incommensurate-normal phase by Rb NMR

The molecular susceptibility and paramagnetic shift of Rb₂CoCl₄ single crystals grown using the slow evaporation method were measured, and from these experimental results we obtained the transferred hyperfine interaction due to the transfer of spin density from Co²⁺ ions to Rb⁺ ions. The transferred hyperfine field was obtained for the ferroelectric, incommensurate, and normal phases. In the case of Rb(I), the transferred hyperfine interaction decreases with increasing temperature in the incommensurate phase, and increases with increasing temperature in the normal phase. The value of H_hf in the incommensurate and normal phases increases abruptly with increasing temperature in the case of Rb(II). These results indicate that the effects due to the transfer of spin density from Co²⁺ ions to the Rb(I) and Rb(II) ions are large above T_i. In particular, the effect due to the transfer of spin density to Rb(II) ions in the normal phase is very large; the variations with temperature of the transferred hyperfine interactions of the Rb(I) and Rb(II) nuclei are more or less continuous in T_c1 and T_i, and are not affected by the ferroelectric-incommensurate-normal phase transitions.     

Mn activated MgSrAl10O17 green-emitting phosphor—A luminescence and EPR study

This paper reports on the luminescence and electron paramagnetic resonance (EPR) investigations on MgSrAl₁₀O₁₇:Mn²⁺ green-emitting phosphor. Single-phase MgSrAl₁₀O₁₇ was successfully synthesized by the one-step solution combustion route without the need for post-annealing at a higher temperature. Crystallization of the powder was confirmed by X-ray diffraction. The luminescence of Mn²⁺- activated MgSrAl₁₀O₁₇ shows a strong green-emission peak around 515 nm due to the ⁴T₁→⁶A₁ transition of Mn²⁺ ions under the excitation (453 nm). The EPR spectra of Mn²⁺ ions exhibit a sextet hyperfine structure centered at g ≈1.995. The Mn²⁺ ion occupies Mg sites which are in tetrahedral symmetry. The magnitude of the hyperfine splitting (A) indicates that Mn²⁺ is in a moderately ionic environment. The number of spins participating in resonance (N), the paramagnetic susceptibility (χ) and the zero-field splitting parameter (D) have been evaluated and discussed.     

Growth, EPR and optical absorption spectra of l-threonine single crystals doped with Cu ions

We investigated the crystal growth, electron paramagnetic resonance (EPR) and optical absorption spectra of l-threonine doped with Cu²⁺. The quality, size and habit of the single crystals grown from aqueous solution by the slow solvent evaporation and by the cooling methods vary when the impurities are introduced during the growth process. The variations with the magnetic field orientation of the EPR spectra of single-crystal samples at room temperature and 9.77 GHz in three crystal planes (ab, bc and ac) show the presence of copper impurities in four symmetry-related sites of the unit cell. These spectra display well resolved hyperfine couplings of the of Cu²⁺ with the I_Cu= of the copper nuclei. Additional hyperfine splittings, well-resolved only for specific orientations of the magnetic field, indicate that the copper impurity ions in the interstitial sites have two N ligands with similar hyperfine couplings. The principal values of the g and A_Cu tensors calculated from the EPR data are g₁=2.051(1), g₂=2.062(2), g₃=2.260(2), A_Cu,1=16.9(5)×10⁻⁴ cm⁻¹, A_Cu,2=21.8(6)×10⁻⁴ cm⁻¹, A_Cu,3=180.0(5)×10⁻⁴ cm⁻¹. The principal directions corresponding to g₃ and to A_Cu,3 are coincident within the experimental errors, reflecting the orientation of the bonding planes of the copper ions in the crystal. The values of the crystal field energies are evaluated from the optical absorption spectrum, and the crystal field and bonding parameters of the Cu impurities in the crystal are calculated and analyzed. The EPR and optical absorption results are discussed in terms of the crystal structure of l-threonine and the electronic structure of the Cu²⁺ ions, and compared with data reported for other systems. The effects of the impurities in the growth and habit of the crystals are also discussed.     

Variable temperature EPR study of Fe2+ spin transition in Cu2+ doped [Fe(trz)(Htrz)2](BF4)

The temperature dependence of the EPR spectrum of Cu²⁺ in the range 293–393 K exhibits a low-spin (S=0) to high-spin (S=2) transition of the Fe²⁺ ions, with hysteresis (T _c↑=363 K,T _c↓=343 K). At 103 K, the principal values of theg and hyperfine tensors of Cu²⁺ ions are revealed by hyperfine structure.     

2 S 1/2-states of Pb3+-ions: Correlations betweeng-values and hyperfine splitting constantsA in the EPR-spectra

The EPR-spectra of the² S _1/2-state of Pb³⁺-ions in different host lattices are characterized by a pronounced hyperfine splitting constantA, a smallg-shift from the free spin valueg _e and an appreciable amount of superhyperfine interaction. The unpaired 6s-electron of the Pb³⁺-ion is predominantly found in molecular orbitals built from the central 6s-function and orbitals of the sorrounding ligand ions. This assumption leads to correct estimates of theg-shift (Watanabe theory) and the reduction ofA due to covalent bonding effects. Theg- andA-values are shown to be correlated.     

Spin-spin and spin-other-orbit effects of optical spectra and the spin-Hamiltonian parameters for Cr ions in MgO crystals

An extended complete diagonalization method/microscopic spin-Hamiltonian (CDM/MSH) program has been developed, which is applicable for d³ ions at sites of tetragonal symmetry type I (C_4v, D_2d, D₄, D_4h) and trigonal symmetry type I (C_3v, D₃, D_3d). The Hamiltonian includes the spin-spin (SS) and spin-other-orbit (SOO) magnetic interactions besides the spin-orbit (SO) magnetic interaction usually taken into account. Utilizing the extended CDM/MSH program, the optical spectra, the spin-Hamiltonian (SH) parameters of the ground state ⁴B₁, and the splitting δ(²E) of the first excited ²E state for Cr³⁺ (3d³) ions at C_4v symmetry sites in MgO crystals have been successfully investigated. It is found that although the SO magnetic interaction is the most important one, the contributions to the SH parameters and the optical spectra from the SS and SOO magnetic interactions for Cr³⁺:MgO crystals are appreciable and should not be omitted, especially reaching 27.8% for the zero field splitting parameter D.     

EPR of Mn4+ in LiF:U,Mn

A new manganese center in LiF single crystals doped with U₃O₈ and MnO₂ has been observed at room and liquid nitrogen temperatures. The trigonal EPR spectrum consists of one very anisotropic fine structure transition with six well-resolved hyperfine components. An analysis of the spectra recorded at X and Q bands shows that the zero field splitting is larger than the electronic Zeeman interaction.By comparing a theoretical calculation of the g values and the hyperfine structure with the experimental X and Q band data it was concluded that the ion is Mn⁴⁺. The presence of Mn⁴⁺ in these crystals confirms an assumption of Runciman regarding the possibility of introducing high valency ions in alkali fluorides containing uranium with an excess of oxygen.     

Investigation of gain and hyperfine splitting in the niobium X-ray laser

Neon-like niobium X-ray lasers have been studied using both slab and thin-foil target geometries. Niobium foils of various lengths were irradiated from both sides with two beams of the frequency-doubled Nova laser system using a line focus. We looked for gain by measuring spectrally integrated line intensities at different plasma lengths. Gain was observed in four neon-like niobium lines corresponding to 3s–3p transitions. The line profile of theJ = 0–1 line ( = 145.9 ) shows splitting due to the hyperfine effect. Improved contrast in the hyperfine structure is observed as the plasma length is increased. Hyperfine splitting may be relevant to other 3s–3p transitions in neon-like niobium as well as other neon-like X-ray laser systems.     

Theoretical study of the KLL dielectronic recombination for highly charged iodine ions

With a developed program for calculation of dielectronic recombination (DR) process, which is based on multi-configuration Dirac-Fock (MCDF) method, the KLL DR processes of the highly charged helium-like to carbon-like iodine ions have been studied systematically. The contributions to doubly excited states from quantum electrodynamic (QED) and Breit effects have been discussed. The KLL DR resonant energies and corresponding resonant strengths have been calculated. The behavior of KLL resonant strengths with increasing Z are analyzed for He-like ions in particular. The theoretical DR spectra for each highly charged ion species are obtained in the KLL region. Comparison has been made between the present calculations and the latest experiments in Tokyo-EBIT.     

237Np Mössbauer spectroscopy on neptunium doped borosilicate glasses

Mössbauer and magnetization measurements have been carried out on borosilicate glasses containing neptunium. Different melting and annealing times, in various crucibles have been investigated. Using the 59.5 keV Mössbauer resonance in²³⁷Np we have characterized valency states of neptunium ions in glasses and studied hyperfine interactions. Roughly, absorption spectra show two sites easily differenciated above 50 K by two lines. Isomer shifts (relative to NpAl₂) are respectively: – 10.0 (1.0) and + 32.5(.5) mm/s. These resonance lines can be assigned, the first at Np⁴⁺, the second at Np³⁺ species. The intensity ratio Np⁴⁺/Np³⁺ varies with elaboration conditions. At 4.2 K, Np⁴⁺ ions exhibit a hyperfine splitting arising from relaxation phenomenon. Magnetization measurements do not show any magnetic ordering.     

Superhyperfine structure in the EPR spectra and optical spectra of impurity f ions in dielectric crystals: A review

The results of observation and simulation of the superhyperfine (ligand hyperfine) structure (SHFS) of the electron paramagnetic resonance (EPR) spectra of rare-earth and uranium impurity ions in dielectric crystals have been systematized. The resolved SHFS of the EPR spectra of doped cubic crystals (with the fluorite and perovskite structures) has been observed for orientations of a constant magnetic field along the crystallographic axes. Most attention has been paid to tetragonal double fluorides LiRF₄ (R = Y, Lu, Tm), in which the SHFS of the EPR spectra has also been found for intermediate orientations of the magnetic field. For the LiYF₄: Nd³⁺ single crystal, the splitting of optical spectral lines due to the interaction of Nd³⁺ ions with nuclear magnetic moments of the nearest neighbor fluorine ions has been observed for the first time. The Van Vleck paramagnet LiTmF₄: U³⁺ is characterized by the SHFS with clearly distinguishable components due to the interaction of uranium ions both with nuclei of the fluorine ions and with enhanced magnetic moments of the thulium nuclei. The SHFS envelopes of the EPR spectra of Yb³⁺, Ce³⁺, Nd³⁺, and U³⁺ ions in LiYF₄ and LiLuF₄ crystals are well reproduced by numerical calculations based on the microscopic model using only three fitting parameters: the width of transitions between the electron-nuclear sublevels of the complex containing the paramagnetic ion and nuclei of the ligands and two constants of covalent bonding of the f electrons with 2s and 2p electrons of the nearest neighbor fluorine ions.