Local structure and the electron paramagnetic resonance parameters for the Cr3+ ions at K+-vacancy site in Cr3+:KZnF3 laser crystal

The quantitative relationship between the electron paramagnetic resonance (EPR) parameters D,g_∥,g_⊥ and the local structure parameters of Cr³⁺ ion in KZnF₃ crystals is established. The local structure for Cr³⁺ paramagnetic center in KZnF₃:Cr³⁺ crystal has been determined from EPR parameters of Cr³⁺ ion. This work shows that the trigonal crystal field of Cr³⁺ ion in KZnF₃ crystals comes from following two origins: (1) the nearest-neighbor K⁺ vacancy caused by the charge compensation in the [1 1 1]-axis direction; and (2) the lattice distortions of the nearest-neighbor fluorine coordination caused by the K⁺ vacancy and the differences in mass, charge, and radius between Cr³⁺ ion and Zn²⁺ ion. The unified calculation of the EPR zero-field splitting and g factors, taking into account the K⁺ vacancy and the lattice distortions, has been carried out on the basis of the complete diagonalization procedure and the superposition crystal-field model, all calculation results are in excellent agreement with the experimental data. Although the main source of the trigonal crystal field comes from the K⁺ vacancy caused by the charge compensation, the contribution of the lattice distortion cannot be neglected.     

Recombination of U 92 + ions with electrons

Recombination of fully stripped U⁹²⁺ ions with electrons has been investigated at the Experimental Storage Ring (ESR) in Darmstadt. Absolute recombination rate coefficients have been measured for relative energies from 0 to 33 eV. For energies greater than 20 meV the experimental result is well described by the theory for radiative recombination (RR). Below 20 meV the experimental rate increasingly exceeds the RR calculation as observed previously in the recombination of light bare ions as well as of Bi⁸³⁺. This low-energy rate enhancement is shown to scale as Z^2.6 for bare ions, where Z is the atomic number of the ion. The U⁹²⁺ recombination rate enhancement is insensitive to changes of the electron density. Variation of the magnetic guiding field strength from 80 mT to 120 mT resulted in oscillations of the recombination rate at 0 eV. The oscillations are partly attributed to changes of the transverse electron temperature accompanying the change of the magnetic guiding field strength; partly they may be caused by uncompensated small changes of the interaction angle between the two beams. Received 1st March 2001 and Received in final form 20 April 2001     

Radiative recombination of ions and nuclei in electron cooling systems

Experimental data on rates for the radiative recombination of nuclei (from helium to uranium) and various ions in interaction with an electron beam in electron cooling systems are reviewed. An analysis of the experimental data has yielded the dependence of the radiative recombination rate on the relative electron energy appreciably differently than the theoretical models obtained earlier by H. Kramers and R. Schuch. In addition, it is shown that the radiative recombination rate of nuclei in the experiment depends on the transverse electron energy as T _?? ^?0.82 ,which is also different from the results of the calculations by the theoretical model proposed by M. Bell and J. Bell. Experimental data on the cooling of ions in intermediate charge states are analyzed and the dependence of the radiative recombination rate on the charge state of the ion (electron-shell configuration) is shown. For some ion charge states, the rate of the process is of a resonance character. Loss to radiative recombination in the electron cooling system of the NICA Booster is evaluated for the Au³²⁺, Au³³⁺, Au⁵⁰⁺, and Au⁵¹⁺ ion beams. Limitations imposed on the Au79+ beam lifetime by radiative recombination in the electron cooling system of the NICA Collider are analyzed. Possible ways to decrease the radiative recombination rate of nuclei by selecting the parameters of the electron cooling system for the NICA Collider are proposed.     

Concentration quenched luminescence and energy transfer analysis of Nd3+ ion doped Ba-Al-metaphosphate laser glasses

This paper reports the dopant ion (Nd³⁺) concentration effects on its luminescence properties in a new glass system based on barium-alumino-metaphosphates. Amongst the studied concentrations range of 0.276–13.31×10²⁰ ions/cm³, the glass with 2.879×10²⁰ ions/cm³ (1 mol%) Nd³⁺ concentration shows intense NIR emission from ⁴F_3/2 excited state, followed by a decrease in emission intensity for further increase in Nd³⁺ ion concentration. The observed luminescence quenching is ascribed to Nd³⁺ self-quenching through the donor-donor migration assisted cross-relaxation mechanism. The microscopic energy transfer parameters for donor-acceptor energy transfer, C _DA, and donor-donor energy migration, C _DD, have been obtained from the theoretical fittings to experimental decay curves and the spectral overlap model respectively. The C _DD parameters (×10^?39 cm⁶/sec) are found to be about three orders greater than that of C _DA (×10^?42 cm⁶/sec) for Nd³⁺ self-quenching in this host, demonstrating that the excitation energy migration among donors is due to the hopping mechanism. The energy transfer micoparameters obtained in the present study are comparable to the values reported for commercially available laser glasses LHG-8 and Q-98.     

Investigations of EPR Parameters of MgTiO3:Cr3+, SrTiO3:Cr3+, and SrTiO3:Mn4+ Crystals

Complete high-order perturbation formulas are established based on charge-transfer (CT) and crystal-field (CF) mechanisms. The electron paramagnetic resonance (EPR) g-factors of MgTiO₃:Cr³⁺, SrTiO₃:Cr³⁺, and SrTiO₃:Mn⁴⁺ crystals are calculated from the formulas. The calculations of the EPR g-factors agree well with the experimental values. The contribution rate of the CT mechanism to EPR parameters increases with increasing valence state of the 3d ⁿ ions in the crystals. For the higher-valence state 3d ³ Mn⁴⁺ ion in the crystals, the elucidation of the EPR parameters rationally involves both CF and CT mechanisms.     

Swift heavy ion induced capacitance and dielectric properties of Ni/n-GaAs Schottky diode

The in-situ capacitance and dielectric properties of 25 MeV C⁴⁺ ion irradiated Ni/n-GaAs Schottky barrier diode (SBD) were studied at 100 kHz in the fluence range 5 × 10¹⁰ – 5 × 10¹³ ions/cm². The investigation shows reduction in capacitance and charge density with increase in ion fluence. Consequent changes were observed in other related parameters like conductance, dielectric constant, dielectric loss, loss tangent and electrical modulus. The results were interpreted in terms of generation of swift heavy ion induced acceptor trap states by electronic energy loss mechanism. Besides, the switch over characteristics of depletion to inversion regions in the CV plot reveals minority carrier recombination centers also. The dispersion and relaxation peaks observed in bias dependent dielectric plots were ascribed to the polarization and relaxation mechanism due to the interfacial trap states. The traps and recombination centers were found to alter the barrier characteristics of the fabricated SBD depending upon the ion fluence.     

EPR, Optical Absorption and Superposition Model Studies of Fe3+-Doped Diammonium Hexaaqua Magnesium Sulfate: A Case of Hyperfine Structure

An electron paramagnetic resonance (EPR) study of Fe³⁺-doped diammonium hexaaqua magnesium sulphate single crystal is carried out at liquid nitrogen temperature. EPR spectrum shows two sites. The spin-Hamiltonian parameters are evaluated from angular variation of observed hyperfine lines. Fe³⁺ ion enters the host lattice substitutionally at site I, replacing Mg²⁺, whereas it enters interstitially at site II. The local site symmetry of Fe³⁺ ion within the host lattice is orthorhombic. An optical absorption study is performed at room temperature. Using the optical absorption spectrum the bands are assigned and the Racah parameters (B and C) and cubic crystal field splitting parameter Dq are determined. The nature of metal–ligand bonding in the crystal is determined using EPR and optical data. Crystal field parameters and zero-field splitting parameters (ZFSPs) are evaluated theoretically for both the sites using superposition model and microscopic spin Hamiltonian together with perturbation equations, respectively. The theoretically evaluated ZFSPs are in good agreement with the experimental values.     

Investigations of the spin-Hamiltonian parameters,optical absorption bands,and local structure for the tetragonal Cu2+ center in Cu2+-doped ZnCdO nanopowder

The spin-Hamiltonian (or EPR) parameters of tetragonal Cu²⁺ octahedral centers in ZnCdO nanopowders are calculated from the high-order perturbation formulas based on the cluster approach. In these formulas, the contributions to spin-Hamiltonian parameters due to the admixture between the d orbitals of dⁿ ion and the p orbitals of ligand ions via covalence effect are considered. The crystal field parameters are calculated from the superposition model and so the optical absorption bands (related to the crystal field energy levels) and local structure of Cu²⁺ octahedral centers in ZnCdO nanopowder are also studied. The calculated spin-Hamiltonian parameters and optical absorption bands are in reasonable agreement with the experimental values. The tetragonal elongation ΔR (=R_//−R_⊥) of Cu²⁺ octahedron in ZnCdO nanopowder due to Jahn–Teller effect is acquired from the calculations. The results are discussed.     

Recombination measurements at low energies with Au49+,50+,51+ at the TSR

Recombination of Au⁴⁹⁺, Au⁵⁰⁺, and Au⁵¹⁺ ions has been studied at the TSR. With Au⁵⁰⁺ ions a storage lifetime of only 2 to 4 s was observed with the magnetically expanded electron beam of the cooler at a density of n_e = 10⁷ cm^-3. This short storage time is a consequence of the highest recombination rate coefficient ever observed with an atomic ion (1.8·10^-6 cm³ s^-1 at zero relative energy E_rel = 0 between electrons and ions). At about 30 meV a huge dielectronic recombination resonance is found with a record small width of only about 15 meV. Such resonances fortuitously occurring near E_rel=0 are probably the main reason for the enhanced recombination rates observed with Au⁵⁰⁺, with Pb⁵³⁺ (in a recent experiment at LEAR) as well as with other complex ions. For Au⁴⁹⁺ and Au⁵¹⁺ the recombination rates are smaller by an order of magnitude. This revised version was published online in August 2006 with corrections to the Cover Date.     

Modeling Spectroscopic Properties of Ni2+ Ions in the Haldane Gap System Y2BaNiO5

Modeling of spin Hamiltonian parameters enables correlation of crystallographic, spectroscopic, and magnetic data for transition ions in crystals. In this paper, based on the crystallographic data and utilizing the point-charge model and superposition model, the crystal field parameters (CFPs) are estimated for Ni²⁺(3d ⁸) ions in the Haldane gap system Y₂BaNiO₅. The CFPs serve as input for the perturbation theory expressions and the crystal field analysis package for microscopic spin Hamiltonian modeling of the zero-field splitting parameters (ZFSPs) D and E. Results of an extensive literature search of the pertinent crystallographic data, experimental ZFSPs, and model parameters are briefly outlined. The modeling aims at verification of the experimental ‘single ion anisotropy’ parameters and explanation of the controversy concerning the maximal rhombic distortion |E/D| ≈1/3 reported for Ni²⁺ ions in Y₂BaNiO₅. The preliminary results call for reanalysis of some magnetic studies of the Haldane gap systems.     

Theoretical evaluation of the electron paramagnetic resonance spin Hamiltonian parameters for the impurity displacements for Fe3+ and Ru3+ in corundum

The impurity displacements for Fe³⁺ and Ru³⁺ in corundum (Al₂O₃) are theoretically studied using the perturbation formulas of the spin Hamiltonian parameters (zero-field splitting and anisotropic g factors) for a 3d⁵ (with high spin S = 5/2) and a 4d⁵ (with low spin S = 1/2) ion in trigonal symmetry, respectively. According to the investigations, the nd⁵ (n = 3 and 4) impurity ions may not locate at the ideal Al³⁺ site but undergo axial displacements by about 0.132 Å and 0.170 Å for Fe³⁺ and Ru³⁺, respectively, away from the center of the ligand octahedron along the C₃ axis. The calculated spin Hamiltonian parameters based on the above axial displacements show good agreement with the observed values. The validity of the results is discussed.     

Resonance Raman study of He+ ion implanted nanostructured ZnS

ZnS nanocrytsals of size ∼2.5 nm were prepared by chemical precipitation technique. Pressed pellets of nanostructured ZnS were implanted with He⁺ ions at doses of 5 × 10¹⁴, 1 × 10¹⁵ and 5 × 10¹⁵ ions/cm². Raman spectra of both unimplanted and He⁺ ion implanted samples were recorded with ultraviolet (UV) excitation. LO, 2LO, 2TO, (LO + TA) and (2TO − TA) modes of ZnS were observed in the resonance Raman spectra of the unimplanted nanostructured ZnS samples. In addition, a surface mode was observed at 294 cm⁻¹. With the implantation of He⁺ ions, the 2TO mode disappeared and 2LO mode became prominent and this observation was attributed to the decrease in band gap of ZnS nanocrytsals due to ion implantation. The exciton–LO phonon coupling strength was determined from the intensity ratio of 2LO to LO modes and it was observed that the exciton–LO phonon coupling strength increases with increase in implantation dose. In the present work, we report for the first time the observation of 2TO mode in the resonance Raman spectrum of nanostructured ZnS and also the modification of exciton–LO phonon coupling strength of semiconductor nanoparticles by ion implantation. Copyright © 2008 John Wiley & Sons, Ltd.     

On the behavior of Ho3+ in LaCl3 and the correlation with its absorption spectra

The crystal field (CF) energies of the electronic ground state of Ho³⁺ ions in a LaCl₃ host have been calculated with the set of CF parameters of Crosswhite et al. The magnetic anisotropy and the average susceptibility have been studied from room temperature down to liquid helium temperature. The g-values and the hyperfine structure parameters have been computed and compared with the experimental values. The Schottky and hyperfine heat capacities have also been determined and some interesting anomalies are predicted. All available observed properties are explained fairly well on the basis of the interaction of the ion with the CF proposed by Crosswhite et al.     

Electron paramagnetic resonance of the Eu2+ ion in SrCl2 at high pressure

This paper reports an EPR study of the effect of hydrostatic pressure (up to 10 kbar) and temperature (300, 77, and 4.2 K) on the spin Hamiltonian parameters of the Eu²⁺ ion in a SrCl₂ cubic crystal. It is found that the b ₄ parameter is related by a power law to the distance from the Cl^?1 ligand (b ₄ ～ R ^?13.5). The pressure and temperature are shown not to be equivalent thermodynamic parameters. Lattice vibrations contribute noticeably to the initial S-ion splitting.     

The fluorescence properties of Yb3+ and Er3+ Co-doped YAl3(BO3)4 powders prepared by sol-gel method

Yb³⁺ and Er³⁺ co-doped YAB powders were prepared by sol-gel method. The structure and fluorescence properties were investigated. XRD pattern indicated that the single phase was obtained at 1150°C and the structure belonged to rhombohedral. Under 379 nm excitation, two emissions around 983 nm and 1531 nm were observed and the effect of Yb³⁺ ion concentration on the emission intensity was discussed. The energy transfer was observed under 930 nm excitation and the energy transfer efficiencies for all samples were calculated. The lifetimes of ² F _5/2 level of Yb³⁺ ion and ⁴ I _13/2 level of Er³⁺ ion were measured and the effect of Yb³⁺ ion concentration on the lifetime was also discussed. The results indicated that there was an additional mechanism for the decay of ⁴ I _13/2 level in powder samples. The Yb³⁺ and Er³⁺ co-doped YAB powders should be a potential candidate for ceramic laser materials.     

Synthesis of nano-sized SiC precipitates in Si by simultaneous dual-beam implantation of C+ and Si+ ions

Nanometer-sized SiC precipitates were synthesized in situ in Si by simultaneous implantation of two ion beams of C⁺ and Si⁺ ions. The results of simultaneous dual-beam implantation are compared with those of sequential dual-beam ion implantation and of single-beam C⁺ ion implantation. Remarkable differences are observed regarding the content and the crystal quality of SiC precipitates as well as the defect structure of the Si substrate. The SiC precipitation during dual-beam synthesis is found to depend on the ion energy of the second beam and on the implantation mode, simultaneous or sequential. For suitable implantation conditions, simultaneous dual-beam synthesis can improve the in situ SiC formation in comparison to the single-beam synthesis. A higher density of SiC precipitates with better crystal quality was observed, whereas their size was not changed. The second ion beam enables a shift in the dynamic equilibrium of constructive and destructive processes for SiC formation. A model is proposed assuming that SiC precipitation preferentially proceeds in regions with vacancy defects. The implantation process itself creates vacancy-dominated and also interstitial-dominated regions. The balance of the local point-defect composition is shifted under the second ion beam. In this way, the conditions for SiC precipitation can be modified. Received: 18 February 2002 / Accepted: 17 May 2002 / Published online: 17 December 2002 RID="*" ID="*"Corresponding author. Fax: +49-351/260-3411, E-mail: koegler@fz-rossendorf.de     

Theoretical studies on the local structure and spin Hamiltonian parameters for the orthorhombic Cu2+ center in LiNbO3

The local structure and spin Hamiltonian parameters (the g factors and the hyperfine structure constants) for the orthorhombic Cu²⁺ center in LiNbO₃ are theoretically studied from the perturbation formulas of these parameters for a 3d⁹ ion in an orthorhombically elongated octahedron. This center is ascribed to Cu²⁺ occupying the Nb⁵⁺ site in LiNbO₃, associated with one nearest neighbour oxygen vacancy V_O along the Z axis. The planar bond lengths are found to suffer the relative variation of about 0.16 Å by compressing and stretching the Cu²⁺–O^2? bonds along the X and Y axes, respectively, due to the Jahn–Teller effect and the charge mismatching substitution of Nb⁵⁺ by Cu²⁺. Meanwhile, the effectively positive V_O can make the central Cu²⁺ displace away from the V_O along the Z axis by about 0.3 Å. The theoretical spin Hamiltonian parameters based on the above local distortions show good agreement with the experimental data.     

Above-barrier enhancement of fusion in the 6He + 209Bi nuclear reaction

The fission cross sections for the ⁶He + ²⁰⁹Bi reaction as functions of the ⁶He-beam energy are measured. The experimental excitation functions for the reaction ²⁰⁹Bi(⁶He, 4n)²¹¹ At are also presented. The ⁶He secondary ion beam is obtained on the basis of the extracted-beam transport system of the U400-M accelerator (the Q4DQ spectrometer). A comparison of the experimental data obtained with available results for the ⁶He + ²⁰⁹Bi reaction shows that a pronounced enhancement of the fission cross sections in the above-barrier energy region is observed in the case of the reaction with the ⁶He beam. In order to fit the results of theoretical calculations to the experimental data, it is necessary to reduce the Coulomb barrier by 15% (20%). This corresponds to an increase of 1.5 (1.6) fm in the parameter r ₀ of the nuclear potential.     

Ab initio and crystal field studies of the Mn4+-doped Ba2LaNbO6 double-perovskite

A detailed study using the ab initio DFT-based calculations of the electronic and optical properties of pure and Mn⁴⁺ doped Ba₂LaNbO₆ is presented in this paper. Comparison of the calculated electronic bands structure, density of states diagrams, and dielectric functions for the pure and doped crystal reveals the changes induced by the Mn⁴⁺ impurity ions. In addition, the energy levels of the Mn⁴⁺ ion in the ordered perovskite Ba₂LaNbO₆ are calculated by the exchange charge model (ECM) of crystal field theory and compared with the experimental data that has been presented in the literature. The calculated Mn⁴⁺ energy levels are in good agreement with the experimental spectra. Additionally, the excitation band shapes of the ⁴A_2g(⁴F)–⁴T_2g(⁴F) and ⁴A_2g(⁴F)–⁴T_1g(⁴F) transitions are modeled to estimate the zero-phonon lines (ZPL) positions and the effective number of phonons, which are involved in the corresponding excitation transition. The results of our calculations yield the crystal field parameter of Dq=1780 cm^?1 and Racah parameters B=670 and C=3290 cm^?1, with C/B=4.9 for the Mn⁴⁺ ion in the double-perovskite Ba₂LaNbO₆.     

EPR of Yb3+ ions in Ba1−xLaxF2+x mixed crystals

Electron paramagnetic resonance (EPR) spectra of impurity Yb³⁺ ions (about 0.1 at.%) in mixed crystals BaF₂(1-x) plus LaF₃(x) have been investigated for different values of the concentrationx at a frequency of about 9.5 GHz by both continuous-wave (CW) EPR and electron spin echo methods. A spectrum of trigonal symmetry with a complex hyperfine structure is observed in “pure” BaF₂:Yb³⁺ (x=0). Upon admixture of small amounts of LaF₃ (x=0.001), additional EPR lines arise with intensities increasing with the increase ofx up to 0.005. These lines are attributed to trigonal centers including two rare-earth ions and two compensating fluorine ions. A further increase ofx results in a decrease of the total EPR spectrum intensity, and atx≥0.05 the CW resonance becomes practically unobservable. This may be due to the formation of rare-earth ion clusters with paramagnetic Yb³⁺ ions occurring in domains with a disordered structure of surroundings resulting in very broad EPR lines, which cannot be registered by CW EPR. Indeed, very broad (not less than 1 KG) EPR lines were observed by the electron spin echo method for concentrationsx<-0.02.