Crystal field and microscopic spin Hamiltonians approach including spin-spin and spin-other-orbit interactions for d and d ions at low symmetry C3 symmetry sites: V in Al2O3

A new module has been developed within the CFA/MSH computer package, which is applicable for d² and d⁸ ions at sites of trigonal symmetry type I (C_3v,D₃,D_3d) and type II (C₃,C_3i), including the ‘imaginary’ CF term. For the first time the spin-spin (SS) and spin-other-orbit (SOO) interactions have also been included in the Hamiltonian. This module enables to study the contributions to the energy levels and the spin Hamiltonian parameters, i.e. zero-field splitting D and g-factors: g_∥ and g_⊥. The contributions arising from the spin-orbit (SO), SS, and SOO interaction as well as those due to the low symmetry CF effects induced by the distortion angle ?, which describes the difference between C₃ and C_3v symmetry, can be studied. As an application of the new module, calculations have been carried out for V³⁺(3d²) ions in α-Al₂O₃ crystal, taking into account for the first time the SS and SOO interactions, and the low symmetry CF effects. The results show that (i) the contributions from the SS and SOO interactions to the energy levels are larger for free V³⁺ ions than those for V³⁺ ions in α-Al₂O₃ crystal, (ii) both the contributions to the SH parameters and the energy levels arising from the SOO interaction are larger than those arising from the SS interaction, (iii) the contributions due to the low symmetry CF effects induced by the distortion angle ? are in general significant, (iv) D and g_⊥ are sensitive to the distortion angle ?, whereas g_∥ is insensitive to ?, and (v) the influence of the lattice distortions on the spectroscopic properties of V³⁺ ion in α-Al₂O₃ is pronounced. It appears important for similar ion-crystal cases to consider the lattice distortions in detailed calculations, which take into account the relevant contributions from the SO, SS and SOO interactions. A good agreement between the theoretical and experimental results has been obtained.     

Impurity centers in a barium titanate ceramic doped with rare-earth ions

The ceramic BaTiO₃ doped with rare-earth ions Y, La, Nd, Sm, Lu, and Dy to 0.1–0.5 at. % was studied in the temperature range 160<T<480 K by ESR. Several ESR spectra were observed. The most intense spectra have g factors close to 5.5 and 1.96. The dependences of their intensity, g factor, and width on the concentration of rare-earth ions and temperature were studied. Analysis of the data obtained made it possible to determine the critical concentration of the rare-earth ions x _c =0.2–0.3 at. %. It is characterized by the fact that for x<x _c or x>x _c all rare-earth ions, except Lu, replace predominantly Ba⁴⁺ or Ti⁴⁺, respectively. Models of paramagnetic centers were established: Fe³⁺-V _O (g≈5.5) and Ti³⁺-Ln³⁺ (g≈1.96), where V _O is an oxygen vacancy and Ln is a rare-earth ion. An abrupt change in axial symmetry to cubic for a Fe₃₊-V _O center at a phase transition from the tetragonal into the cubic phase was observed for the first time. The role of new centers in the appearance of the posistor effect is discussed. Fiz. Tverd. Tela (St. Petersburg) 41, 1838–1842 (October 1999)     

Rotational and vibrational relaxation of the NO3 - ion in molten binary systems (M,Ag)NO3 (M = Li,Na and K) by Raman spectroscopy

Polarized and depolarized Raman scattering spectra for the totally symmetric stretching υ₁ mode of nitrate ions (D_3h symmetry) in the molten binary systems (M1,Ag)NO₃(M1= Li, Na, and K) have been measured. Vibrational and rotational autocorrelation³ functions, C_v(t) and C_r(t), respectively, have been evaluated from Fourier transformation of the spectra. The shifts in the peak frequencies are deeply correlated with the polarizability of silver in these mixtures. The vibrational relaxation rate increases with increasing mole fraction of silver nitrate in (K,Ag)NO₃, but does not vary so much in (Li,Ag)NO₃ and (Na,Ag)NO₃. The vibrational relaxation time negatively deviates from additivity on the order of (Na,Ag)NO₃&lt; (Li,Ag)NO₃&lt; (K,Ag)NO₃. In the systems (Na,Ag)NO₃ and (K,Ag)NO₃ rotational relaxation time becomes slower with increasing concentration of AgNO₃. The Ag⁺ coordinating to several nitrate ions in these mixtures appreciably restricts the rotational motion of the nitrate ions. On the other hand, rotational motion becomes easier in the mixture system (Li,Ag)NO₃ mainly because the different preferential sites of the two cations coordinating to an NO₃ ^-ion, and partly because the exchange rates of these cations around the NO_-3 ^-ion are high.     

Electron paramagnetic resonance of Dy3+ ions in lead thiogallate single crystals

The results of electron paramagnetic resonance (EPR) studies of Dy³⁺ ions in lead thiogallate PbGa₂S₄ single crystals have been presented. It has been shown that the ground state of these ions corresponds to the lowest Stark sublevel Γ₆ of the term ⁶ H _15/2. The spectra are well described by the axially symmetric spin Hamiltonian with the effective spin S = 1/2 with the factors g _‖ = 15.06 and g _⊥ = 2.47. The Dy³⁺ ions substitute Pb²⁺ ions in the crystal lattice of PbGa₂S₄. The observed hyperfine structure has allowed to unambiguously interpret the EPR spectra. The hyperfine interaction constants of two odd isotopes of dysprosium in lead thiogallate single crystals have been found to be A _‖ = 675 × 10^?4 cm^?1 and A _⊥ = 111 × 10^?4 cm^?1 for ¹⁶³Dy and A _‖ = 472 × 10^?4 cm^?1 and A _⊥ = 77 × 10^?4 cm^?1 for ¹⁶¹Dy.     

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.     

EPR and optical absorption studies of Fe ions in sodium borophosphate glasses

Electron paramagnetic resonance (EPR) and optical absorption spectral investigations have been carried out on Fe³⁺ ions doped sodium borophosphate glasses (NaH₂PO₄-B₂O₃-Fe₂O₃). The EPR spectra exhibit resonance signals with effective g values at g=2.02, g=4.2 and g=6.4. The resonance signal at g=4.2 is due to isolated Fe³⁺ ions in site with rhombic symmetry whereas the g=2.02 resonance is due to Fe³⁺ ions coupled by exchange interaction in a distorted octahedral environment. The EPR spectra at different temperatures (123-295 K) have also been studied. The intensity of the resonance signals decreases with increase in temperature whereas linewidth is found to be independent of temperature. The paramagnetic susceptibility (χ) was calculated from the EPR data at various temperatures and the Curie constant (C) and paramagnetic Curie temperature (θ_p) have been evaluated from the 1/χ versus T graph. The optical absorption spectrum exhibits bands characteristic of Fe³⁺ ions in octahedral symmetry. The crystal field parameter (Dq) and the Racah interelectronic repulsion parameters (B and C) have also been evaluated and discussed.     

Pd☎ Ions In NaCl Single Crystal: EPR and Optical Studies

EPR and optical absorption of Pd centres in as grown NaCl single crystal arc reported. The EPR spectra show that palladium forms the Pd^? centre with d_x2-y2 wave function in the ground state. This centre formation and the accompanying distortion give rise to a superhyperfine interaction of the Pd^? ion with the nuclei of the four Cl^? ligands in the plane perpendicular to the C₄ symmetry axis. The results of the fitting of axial spin Hamiltonian parameters to the experimentally observed spectra give the following values at 12K: g∥ =2.85, g ⊥ ? 2.15, A ∥29.8 × 10^?4cm^?1, A ⊥ = 5.9 7imes; 10^?4cm^?1. When the temperature increases, lines are getting broader, their amplitude decreases and a single line with g-value of g= 2.38 at g = 1/3(g∥ ?2g⊥) appears, which demonstrates the known Jahn-Teller behaviour of d⁹ ions EPR spectra.     

“Crystal fields” for magnetic ions in metals from itinerant electrons

The interaction of conduction electrons with host ions are shown to give rise to “crystal fields”, V_C, which act on the magnetic ion in some dilute magnetic alloys. Crystal fields, V_N, arising directly from ions neighbouring the magnetic ion have been compared with V_C to show that the overall crystal field splitting from all 3d magnetic ions in axial symmetries is enhanced by the p-like character of V_C. A⁰₄〈r⁴〉 from V_N is also increased by the d-component of V_C. The angular properties of itinerant electron states give rise to the above results. For all rare-earth ions in fcc symmetry the radial and angular components of conduction-electron states with mainly d, but also f character, are shown to give rise to a reversal in sign of A⁰₄〈r⁴〉 from V_N. A⁰₆〈r⁶〉 is enhanced by the f component of the conduction electrons.     

Spectral studies on Cr ions doped in sodium-lead borophosphate glasses

Electron paramagnetic resonance (EPR), optical absorption and emission spectra of Cr³⁺ ions doped in (30−x) (NaPO₃)₆+30PbO+40B₂O₃+xCr₂O₃ (x=0.5, 2.0, 3.0, 4.0 and 5.0 mol%) glasses have been studied. The EPR spectra exhibit resonance signals with effective g values at g≈4.55 and g≈1.97. The EPR spectra of x=3.0 mol% of Cr₂O₃ in sodium-lead borophosphate glass sample were studied at various temperatures (295-123 K). The intensity of the resonance signals increases with decrease in temperature. The optical absorption spectrum exhibits four bands characteristic of Cr³⁺ ions in octahedral symmetry. From the analysis of the bands, the crystal-field parameter Dq and the Racah interelectronic repulsion parameters B and C have been evaluated. The emission spectrum exhibit one broad band characteristic of Cr³⁺ ions in octahedral symmetry. This band has been assigned to the transition ⁴T_2g (F)→⁴A_2g (F). Correlating EPR and optical data, the molecular bonding coefficient (α) has been evaluated.     

Measuring the solubility of benzoic acid in room temperature ionic liquids using chronoamperometric techniques

The electrochemical reduction of benzoic acid (BZA) has been studied at platinum micro‐electrodes (10 and 2 µm diameters) in acetonitrile (MeCN) and six room temperature ionic liquids (RTILs): [C₂mim][NTf₂], [C₄mim][NTf₂], [C₄mpyrr][NTf₂], [C₄mim][BF₄], [C₄mim][NO₃] and [C₄mim][PF₆] (where [C_nmim]⁺ = 1‐alkyl‐3‐methylimidazolium, [NTf₂]^? = bis(trifluoromethylsulphonyl)imide, [C₄mpyrr]⁺ = N‐butyl‐N‐methylpyrrolidinium, [BF₄]^? = tetrafluoroborate, [NO₃]^? = nitrate and [PF₆]^? = hexafluorophosphate). Based on the theoretical fitting to experimental chronoamperometric transients in [C₄mpyrr][NTf₂] and MeCN at several concentrations and on different size electrodes, it is suggested that a fast chemical step preceeds the electron transfer step in a CE mechanism (given below) in both RTILs and MeCN, leading to the appearance of a simple one‐electron transfer mechanism. The six RTIL solvents and MeCN were saturated with BZA, and potential‐step chronoamperometry revealed diffusion coefficients of 170, 4.6, 3.2, 2.7, 1.8, 0.26 and 0.96 × 10^?11 m² s^?1 and solubilities of 850, 75, 78, 74, 220, 2850 and 48 mM in MeCN and the six ionic liquids, respectively, at 298 K. The high solubility of BZA in [C₄mim][NO₃] may suggest a strong interaction of the dissolved proton with the nitrate anion. Although there are relatively few literature reports of solubilities of organic solutes in RTILs at present, these results suggest the need for further studies on the solubilities of organic species (particularly acids) in RTILs, because of the contrasting interaction of dissolved species with the RTIL ions. Chronoamperometry is suggested as a convenient methodology for this purpose. Copyright © 2008 John Wiley & Sons, Ltd.     

Study of sensitization of Cr4+ ions by Yb3+ ions in yttrium-aluminum garnet crystals

The possibility of using ytterbium ions as sensitizers of luminescence of tetravalent chromium in yttrium-aluminum garnet single crystals is studied. It is found that average values of the microparameters of electronic energy transfer between ytterbium and chromium ions are C _DA=7.05×10^?36 cm⁶/s and C _DD=4.55×10^?43 cm⁶/s.     

Surface modifications of crystalline SiO2 and Al2O3 induced by energetic heavy ions

Abstract

Glasses with composition × CoO.(0.25-x) CaO.0.75 B₂O₃ have been prepared over the range 0 ≤ x ≤ 0.25 containing 2 mol% of V₂O₅. Electron paramagnetic Resonance spectra of VO²⁺ of these glasses has been measured at X-band (ν ≈ 9.15 GHz) at room temperature and at liquid nitrogen temperature. Spin Hamiltonian parameters of the VO²⁺ ions have been calculated. It is found that for x ≤ 0.12 the octahedral symmetry of the V⁴⁺ site is improved. A part of these glasses were annealed at 473 K for 24 hours and EPR spectra were recorded and analysed.     

Kinetics of the oxidation of model toxicants during photolysis of nitrites and nitrates in an aqueous medium

Quantitative toxicology methods with the use of the enzymic activity of luminescent bacteria and the reproductive function of Tetrahymena pyriformis infusoria as test functions were employed to study the kinetics of the detoxication of model toxicants during photolysis of nitrite and nitrate. The model objects were the para-nitrosodimethylaniline (p-NDA) dye and a 2000-fold diluted solution of black liquor, which is formed during the sulfate boiling of cellulose. It was established that, irrespective of the wavelength of photolyzing UV radiation, be it 220 or 365 nm, the reactive product of NO ₂ ^? and NO ₃ ^? photolysis is the hydroxyl radical, which causes a symbatic decrease in the concentration of the toxicant and its toxicity. It was demonstrated that nitrite and nitrate ions can be used as initiators of free radicals during the destructive UV-light-induced purification of wastewater.     

NO 3 2− and CO 2 − centers in synthetic hydroxyapatite: Features of the formation under γ- and UV-irradiations

The EPR studies of synthetic hydroxyapatite containing carbonate and nitrate ions exposed to γ-ray and UV irradiations have been performed. It has been found that γ irradiation leads to the formation of both NO₃²⁻ and CO₂⁻ paramagnetic centers, while the UV irradiation induces only NO₃²⁻ centers. To explain this fact, the hypothesis has been proposed, according to which in the hydroxyapatites studied, there coexist complexes consisting of nitrate ions and shallow electron traps that serve as sources of secondary electrons during UV irradiation. The EPR spectroscopy parameters (g and A) of the detected centers have been determined and compared with similar centers in hydroxyapatite with a different impurity composition. The study of the thermal stability of the centers has demonstrated that, in the temperature range 20–300°C, the NO₃²⁻ centers formed by UV irradiation are more stable than the same centers created by γ-ray irradiation.     

Pulse radiolysis studies of 2‐ and 3‐hydroxybenzyl alcohols: inhibition of dehydration of ·OH‐(hydroxybenzyl alcohols) adducts by H2PO4− ions

Reactions of ·OH/O ^.? radicals and H‐atoms as well as specific oxidants such as Cl₂^.? and N₃· radicals have been studied with 2‐ and 3‐hydroxybenzyl alcohols (2‐ and 3‐HBA) at various pH using pulse radiolysis technique. At pH 6.8, ·OH radicals were found to react quite fast with both the HBAs (k = 7.8 × 10⁹ dm³ mol^?1 s^?1 with 2‐HBA and 2 × 10⁹ dm³ mol^?1 s^?1 with 3‐HBA) mainly by adduct formation and to a minor extent by H‐abstraction from ? CH₂OH groups. ·OH‐(HBA) adduct were found to undergo decay to give phenoxyl type radicals in a pH dependent way and it was also very much dependent on buffer‐ion concentrations. It was seen that ·OH‐(2‐HBA) and ·OH‐(3‐HBA) adducts react with HPO₄^2? ions (k = 2.1 × 10⁷ and 2.8 × 10⁷ dm³ mol^?1 s^?1 at pH 6.8, respectively) giving the phenoxyl type radicals of HBAs. At the same time, this reaction is very much hindered in the presence of H₂PO ions indicating the role of phosphate ion concentration in determining the reaction pathway of ·OH adduct decay to final stable product. In the acidic region adducts were found to react with H⁺ ions. At pH 1, reaction of ·OH radicals with HBAs gave exclusively phenoxyl type radicals. Proportion of the reducing radicals formed by H‐abstraction pathway in ·OH/O ^.? reactions with HBAs was determined following electron transfer to methyl viologen. H‐atom abstraction is the major pathway in O ^.? reaction with HBAs compared to ·OH radical reaction. H‐atom reaction with 2‐ and 3‐HBA gave transient species which were found to transfer electron to methyl viologen quantitatively. Copyright © 2010 John Wiley & Sons, Ltd.     

Local structure of the trigonal defect center for Cr3+ ions in KMgF3 crystals

Abstract

The zero-field splitting D, the anisotropic g-factors g _∥, Δg(=g _∥ ? g _⊥) and the first excited state splitting Δ(² E) for the trigonal Cr³⁺–V_K center in KMgF₃: Cr³⁺ crystals have been studied from Macfarlane's high-order perturbation formulas. From the studies, the local structure of the trigonal center is obtained. The local lattice distortions (i.e., the displacement directions of the ions in the center) are consistent with the expectation based on the electrostatic interaction.     

Paramagnetic resonance in irradiated Sr(NO3)2 single crystal

Paramagnetic resonance absorption of centres with spin 1/2 centered aboutg=2 is reported in gamma-irradiated single crystals of Sr(NO₃)₂. At room temperature four centres are detected which appear to exhibit axial symmetry about the [111] crystal direction. Two of the observed centres have a resolved hyperfine structure of N¹⁴. This hyperfine structure and axial symmetry of the centres indicate that they could be irradiation products of the nitrate ion. To find the number of trapped electrons, a simplified calculation of the molecular orbitals of planar and pyramidal NO₃ is carried out. Centres with a resolved hyperfine structure are then identified as pyramidal NO ₃ ^? and a NO₂ molecule rotating about the [111] direction. Two centres without hyperfine structure are not identified exactly.     

Crystal-field hamiltonian and spin-orbit interaction for d and d ions at low C3 symmetry sites: V:Al2O3 and Ni:LiNbO3

The experimental studies have provided evidence of the occurrence of transitions from the ³T_1g(³F) ground state to the crystal-field levels ³T_2g(³F), ³T_1g(³P) and ³A_2g(³F) for the V³⁺ centres in Al₂O₃ crystal; and from the ³A_2g(³F) ground state to the crystal-field levels ³T_2g(³F), ³T_1g(³F) and ³T_1g(³P) for the Ni²⁺ centres in LiNbO₃ crystal (levels are assigned to irreps of the O_h point symmetry group). Using the experimental spectroscopic data, theoretical calculations of the crystal-field levels of V³⁺:Al₂O₃ and Ni²⁺:LiNbO₃ are carried out based on the Racah theory. The observed crystalline-field splittings of the V³⁺ and Ni²⁺ terms were accounted for using a C₃ symmetry Hamiltonian. The spin-orbit interaction was taken into account in this work. The Racah, crystal-field and spin-orbit parameters, which fit experimental and theoretical energy levels, have been reliably obtained. A good agreement between the theoretical and experimental results for the energy levels of V³⁺:Al₂O₃ and Ni²⁺:LiNbO₃ has been obtained.     

Formation of doubly charged negative ions under the conditions of the resonant electron capture by fluorofullerenes

Doubly charged negative ions formed when electrons with controlled energies interact with isolated fluorinated fullerene molecules C₆₀F _n (n = 36, 48) have been detected and investigated by resonant electron capture mass spectrometry. The dependence of the intensity of the formation of doubly charged negative ions of fluorofullerenes on the energy of attached electrons has been measured. An original method, which is based on the experimental data and does not require additional calibration quantities, has been developed for estimating the absolute cross section for the formation of doubly charged negative ions. The absolute cross sections for the formation of the most intensely formed ions C₆₀F ₃₆ ^2? and C₆₀F ₄₈ ^2? are estimated to be about 1.1 × 10^?24 and 1.5 × 10^?24 m² at their maximum-yield energies of 2.0 and 1.6 eV, respectively.     

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.