Zeeman splitting factor of the Er3+ ion in a crystal field

Numerical computations are presented on the energy levels of the Er³⁺ ion in crystalline fields of cubic, trigonal, tetragonal and orthorhombic symmetry. Zeeman splitting factors were obtained from the level splitting in an additional magnetic field. For the quartet Γ₈ states in cubic symmetry the Zeeman effect is described by an effective Hamiltonian ℋ= gμ_BBJ+ uμ_BBJ³ with the parametersg andu calculated for mixed fourth- and sixth-order potentials. For the eight doublets in the lower symmetry of an axial trigonal or tetragonal crystal field the principalg tensor components g_∥ and g_⊥ were calculated. The results of such calculations for a ground-state doublet can exactly account for the experimental data obtained on around 70 erbium centers in various crystalline hosts. However, sometimes different sets of parameters give comparably good results. An empirical rule of constant trace g_∥ + 2g_⊥ is supported by the calculations. In contrast to analytical treatments the effect of the crystalline field can be followed over a continuous range of the crystal field parameters. This allows one to establish relations on the relative signs of tensor components. It is found that the measured trace of tensors |g_∥| + 2|g_⊥| is not always equal to their real trace g_∥ + 2g_⊥. In an exploratory calculation a nonaxial center was simulated in an orthorhombic field, with calculation of the three principal values g_x, g_y and g_z. A good agreement is obtained for the recently reportedg values of an erbium center in silicon.     

EPR investigations of Cu(II) complexes with 5′-CMP and 5′-GMP

Electron paramagnetic resonance investigation of the Cu(II) complexes with guanosine-5′-monophosphate (5′-GMP) and cytidine-5′-monophosphate (5′-CMP) shows the affinity of the Cu(II) ion to interact with the base and the phosphate group. The different modes of the coordination of the metal ion at the nucleotide and the water molecules lead to octahedral species, distorted by dynamical Jahn-Teller effect (g₀ = 2.106) for the Cu(II)-5′-CMP complex and rhombically distorted (g₁ = 2.358, g₂ = 2.126, g₃ = 2.068) or tetragonally distorted (g_∥^′ = 2.299, g_⊥^′ = 2.126) for the Cu(II)-5′ -GMP complex. The compound with 5′-CMP presents also a more stable in time square-planar species (g_∥ = 2.265, A_∥ = 162 G, g_⊥ = 2.076). The local symmetry changes in aqueous solution by coordination of water molecules.     

Electron paramagnetic resonance of NH 3 + radical in potassium sulphate

Room temperature EPR spectra of (NH₄)₂SO₄ doped K₂SO₄ monocrystals irradiated with x-rays show the presence of NH₃ ⁺ radicals. The EPR parameters areg ‖=2.0037 andg ⊥ = 2.0068;¹⁴NA _XX=13.75;A _YY=24.5;A _ZZ=25.5 gauss;¹HA _XX=A _YY=22 andA _ZZ=25 gauss. From the¹⁴N and¹H coupling constants it has been inferred that at room temperature the planar NH₃ ⁺ radical undergoes rotation about theC ₃ axis which corroborates with the equivalence of the protons, but the radical itself is in an asymmetric crystal field environment. The 77K spectra indicate a considerable reduction in the motion of the radical with the free motion almost completely stopped. Part of Ph.D. work of the second author     

Transient EPR at 240 GHz of the excited triplet state of free-base tetra-phenyl porphyrin

The electron paramagnetic resonance (EPR) spectrum measured at 240 GHz of the lowest excited triplet state of the free-base tetra-phenyl porphyrin (H₂-TPP) molecule is presented. The high frequency that is employed allows for the full resolution of theg-anisotropy (2.00354(2), 2.00272(15), and 2.00194(5) forx, y, andz zero-field axes respectively), and the obtained values are compared to those of other porphyrin-based systems. These results are one of the first addressing theg-anisotropy in the photoexcited state of porphyrins. The usefulness of high-field transient EPR in elucidating not only the principal values of theg-tensor but also the orientation of theg-tensor principal axes with respect to those of the zero-field splitting tensor in porphyrin disordered systems is also discussed.     

Ellipsometric spectroscopy of the ZnO nonpolar(1\bar 100) surface

Ellipsometric spectroscopy has been performed on nonpolar ZnO surfaces in the spectral range 1.5 eV<ħω<4.0 eV. Absolute measurements with two different crystal orientations in air allow the determination of the optical constantsn _∥,k _∥ andn _⊥,k _⊥ for light polarized parallel and perpendicular to thec-axis. The ellipsometric angles Δ and ψ are changed remarkably on ultrahigh vacuum cleaved surfaces near the band gap energy of ∼3.4eV when oxygen or atomic hydrogen is adsorbed or when the crystal is annealed. This observation is interpreted in terms of a field effect on the optical constants in the space charge layer.     

Superconductivity and magnetic order in CaLaBaCu3O z

X-ray diffraction, thermogravimetric analysis, magnetization and Mossbauer studies of a⁵⁷Fe probe, in CaLaBa(Cu_1−x Fe _x )₃O _z withz=7, 6.5 andx=0.00 to 0.05 have been performed. Forz=7,T _c drops from 74 K forx=0.00 to 35 K forx=0.05. In CaLaBa(Cu_1−x Fe _x )₃O _z withz=7, 10% of the iron is magnetically ordered withH _eff=530 K kOe andT _N=400 K, even though the sample is superconducting. In the oxygen poor, non-superconducting samples (z=6.5) 20% of the iron is magnetically ordered withH _eff=340 kOe andT _N=340 K. Since the iron reflects the magnetic order of the Cu(2) ions, this may show that perhaps two inequivalent Cu(2) sites exist in CaLaBa(Cu_1−x Fe _x )₃O₇, ones of which is magnetically ordered. The experimental observations may be interpreted in terms of the special crystal structure which can allow superconductivity and magnetism to coexist, probably in separate Cu(2) planes.     

Intersectingp — p′ branes inpp-wave background

Several supergravity solutions corresponding to bothDp, as well asDp—Dp′ systems, inNS-NS andR-R pp-wave background originating fromAdS ₃ xS ³ xR ⁴ are presented. The supersymmetry properties of these solutions are analysed along with a brief outline of the world sheet construction for thep — p′ branes.     

Structural phase transition in substituted La2CuO4 and Pr2CuO4−y

The structural phase transition from orthorhombic (T) phase to tetragonal (T′) phase in substituted La_2−x R _x CuO₄ (R = Pr, Nd, Sm, Eu and Gd) and T′ to T-phase in Pr_2−x M _x CuO_4−y (M = Sr, Ca) has been studied by X-ray diffraction technique. The T-phase of La₂CuO₄ is transferred to T′ phase abruptly atx=0.8, 0.4, 0.4, 0.3 and 0.4 respectively for substitution of Pr, Nd, Sm, Eu and Gd for La in La₂CuO₄ without evidence of the T* phase. The T′ structure of Pr₂CuO₄ (x = 0.0) gets transformed to the T* structure at 30% Ca doping (x=0.6) and then to the T structure at 50% Ca doping (x=1.0), while for Sr-contentx=0.0, 0.4 and 1.0 it shows T′, T* and T structure respectively.     

Studies of local phase transition behavior for Co2+ in CsCaCl3 crystals from EPR data

In this paper, we establish the calculation formulas ofg factorsg _∥,g _⊥ and the hyperfine structure constantsA _∥,A _⊥ for 3d⁷ ions in tetragonal octahedral field from a cluster approach. In these formulas, besides the configuration interaction, the covalency effect due to the admixture between d electrons of 3d⁷ ion and the p electrons of ligands is considered. The parameters used in these formulas (except the core polarization constantsk in the calculation ofA _i) can be obtained from optical spectra of the studied crystal. From these formulas, the local release (or elongation) factork, which is introduced to characterize the release effect of impurity-ligand bond along C₄ axis at the cubic to tetragonal phase transition, is estimated for CsCaCl₃:Co²⁺ crystal by calculating the electronic paramagnetic resonance (EPR) parametersg _i andA _i . These EPR parameters are therefore explained reasonably and the results are discussed.     

Coexistence of one-electron- and monoprotonated two-electron-reduced species of the K5[PMo2VW9O40] · 24H2O heteropolyoxometalate identified by EPR

The simulation of the room-temperature experimental electron paramagnetic resonance spectrum of K₅[PMo₂VW₉O₄₀] · 24 H₂O heteropolyoxometalate indicates the presence of equal amounts of a one-electron-reduced species (g _∥ = 1.922,g _⊥ = 1.972,A _∥ = 181 G,A _⊥ = 63 G) and a monoprotonated two-electron-reduced species with mixed-valence V^IV, Mo^V and Mo^VI ions (g _iso = 1.972, ΔB _iso(p-p) = 450 G). Two unprotonated one-electron-reduced isomers are identified in dimethylsulfoxide-H₂O solution of the sample atT = 100 K (g _∥¹ = 1.929,g _⊥¹ = 1.990,A _∥¹ = 179 G,A _⊥¹ = 65 G andg _∥² = 1.918,g _⊥² = 2.000,A _∥² = 187 G,A _⊥² = 80 G, respectively). The values of the in-plane π(V−O) bond π₂² coefficient for the one-electron-reduced species (0.87 at room temperature and 0.83 and 0.74 for the species in frozen solution) suggests the delocalization of the vanadium unpaired electron towards the molybdenum ions via O_b atoms.     

Paramagnetic defects in neutron-irradiated phenakite crystals

Radiation-disordered crystals of phenakite Be₂SiO₄ (at fast neutron fluences of (0.75, 1.0, 1.2, 6.6, 8.5) × 10¹⁸ cm⁻²) have been investigated using EPR spectroscopy. It has been established that the main radiation damages predominantly occur in the silicon-oxygen sublattice of the crystal. Vacancy centers (E′ centers, g = 2.0015), defects of the displaced oxygen type, and O⁻ hole-type centers have been revealed. The paramagnetic absorption signal with the parameters g _x = 2.0218, g _y = 2.0124, and g _z = 2.0027 has been identified with the [SiO₄]³⁻ complex (a variety of O⁻ centers). The intense EPR signals with the parameters g _x = 2.0526, g _y = 2.0020, g _z = 2.0066 and g _x = 2.0290, g _y = 2.0030, g _z = 2.0099 have been assigned to two types of O₂⁻ molecular ions with different local environments. The theoretical models of radiation-induced centers have been discussed by comparing the EPR and optical spectroscopic data.     

ESR of V4+ in α-RbTiOPO4 single crystals

We have recorded and investigated the ESR spectrum of vanadium-doped α-RbTiOPO₄ single crystals in the temperature interval 77–300 K. Two types of structurally distinct centers, V1 and V2, with a 4:1 ratio of the peak intensities were observed. The angular dependences of the resonance magnetic fields are described by a spin Hamiltonian corresponding to axial symmetry with the parameters g _∥1=1.9305, g _⊥1=1.9565, A _∥1=−168.2×10⁻⁴cm⁻¹, and A _⊥1=−54.3×10⁻⁴cm⁻¹ for V1 centers and g _∥2=1.9340, g _⊥2=1.9523, A _∥2=−169.0×10⁻⁴cm⁻¹, and A _⊥2=−55.2×10⁻⁴cm⁻¹ for V2 centers. A model of a paramagnetic center is proposed: The vanadium ions replace titanium ions in two structurally distinct positions Ti1 and Ti2 (V1 and V2 centers, respectively). The possibility that a VO²⁺ ion forms when α-RbTiOPO₄ crystals and crystals of the KTP group (KTiOPO₄, NaTiOPO₄, α-and β-LiTiOPO₄), studied earlier, are doped with vanadium is discussed. Fiz. Tverd. Tela (St. Petersburg) 40, 534–536 (March 1998)     

Strontium Tetraborate Glasses Doped with Transition Metal Ions: EPR and Optical Absorption Study

Electron paramagnetic resonance (EPR) and optical studies have been carried out on Cu(II)-, VO(II)- and Cr(III)-doped strontium tetraborate glasses to understand the distortion and substitution of these ions. The EPR results of Cu(II) glass indicate that g _∥ > g _⊥, typical for the tetragonally elongated octahedral site of the Cu(II) impurity. The evaluated covalency parameter 0.788 suggests a moderate covalency for the bonding. By correlating EPR and optical results, the in-plane π-bonding β₁ ² is evaluated as 0.715. In the vanadium-doped glasses, the distortion must be a tetragonally elongated octahedron, similar to Cu(II). However, the EPR studies show that g _⊥ > g _∥ indicating the tetragonally compressed octahedral site for the ion. The site symmetry is C _4V. Supported by the optical absorption, evaluated parameters propose a moderate covalency. The EPR and optical results for Cr(III) glass indicate the distorted octahedral site symmetry in the host lattice. These results further suggest that the bonding between Cr(III) and the ligands is covalent. Authors' address: Renduchintala V. S. S. N. Ravikumar, Department of Physics, Acharya Nagarjuna University, Nagarjuna Nagar 522510, India     

Electron beam irradiation induced changes in liquid-crystal compound 5CB

Electron beam irradiation studies on liquid crystal material 5CB have been carried out at a temperature where the compound exists in the isotropic liquid phase. In situ time-resolved spectroscopic characterization was carried out during the irradiation. Three different transients were observed during the 2-μs electron pulse. After about 50 μs, only one transient species was found to be present, which has an absorption peak at 360 nm. Radiolysed sample exhibits a broad absorption at ∼400 nm. The dielectric measurements show that even a low level of irradiation results in a dramatic increase in the component of dielectric permittivity normal to the long axes of the molecules ε_⊥^′, and a corresponding decrease in the dielectric anisotropy (Δε′=ε_∥^′−ε_⊥^′ ). These studies show that 5CB is prone to substantial radiation damage on exposure to the beam of high-energy electrons.     

ESR study of exchange coupled pairs in copper diethyldithiocarbamate

ESR investigations on exchange coupled pairs of Cu ions in single crystals of Cu(dtc)₂, isomorphously diluted with the corresponding diamagnetic zinc salt, are reported. The spin Hamiltonian parameters for the coupled species (S=1) are:g _‖=2.1025,g ₊=2.031,A=75.1×10⁻⁴ cm⁻¹,B=14.8×10⁻⁴,D=276.0×10⁻⁴ cm⁻¹ andE=46.7×10⁻⁴ cm⁻¹. While theg andA tensors show tetragonal symmetry, the zeor-field splitting tensor is rhombic and has principal axes different from those of theg andA tensors. Intensity measurements made down to 4.2 K indicate that the exchange is ferromagnetic with |FFF| ∼ 10 cm⁻¹. Direct dipole-dipole interaction appears to be the major contribution to the zero-field splitting. A calculation on the distributed point dipole model shows that dipolar interaction is considerably modified by the high covalency of the Cu-S bond and accounts for the rhombic nature of the tensor. The possible exchange mechanisms in Cu(dtc)₂—direct exchange and superexchange through the bridging sulphurs—are discussed.     

EPR and Optical Study of Cu<Superscript>2+</Superscript> Ions Doped in Sodium Zinc Sulfate Tetrahydrate Single Crystals

Electron paramagnetic resonance (EPR) study of Cu²⁺-doped sodium zinc sulfate tetrahydrate is done at liquid nitrogen temperature. Two magnetically equivalent sites for Cu²⁺ are observed. The spin-Hamiltonian parameters determined by fitting the EPR spectra to the rhombic-symmetry crystalline field are g _x  = 2.2356, g _y  = 2.0267, g _z  = 2.3472, A _x  = 27 × 10⁻⁴ cm⁻¹, A _y  = 54 × 10⁻⁴ cm⁻¹and A _z  = 88 × 10⁻⁴ cm⁻¹. The ground state wave function is also determined. The g-anisotropy is evaluated and compared with the experimental value. With the help of optical study, the nature of bonding in the complex is discussed.     

Calculation of chemical bonds and diffusion path of Li ion in (LaLi)Ti2O6 by DV-Xα cluster method

The chemical bonds and lithium diffusion of La_4/3−y Li_3y Ti₂O₆ (y = 0.21) were investigated by using the DV-Xα cluster method. The cluster model used is the formula La₈Li₂Ti₂O₁₁. A Li ion was moved on the ab plane at z = 1/2. The Na ion was moved along the x axis in the cluster model La₈Na₂Ti₂O₁₁ for comparison. The total bond overlap population (BOP) between the moving Li ion and the other ions was calculated on the ab plane at z = 1/2. The total BOP of the Li ion along the x axis increased near the oxygen ion site, whereas the BOP of the Na ion decreased. The decrease in total BOP indicates the decrease in covalent interaction between the Na and the other ions. The change of the net charge of the Li ion was almost the same as that of the Na ion. This suggests that the smaller change of covalent interaction in the mobile Li ion determines the diffusion path of Li ion.     

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.     

Overall values of conventional discrepancy indices for crystals with heavy atoms. Part II. Results for monoclinic and orthorhombic crystals when the heavy-atom part alone constitutes the model

Theoretical expressions of 〈y _N〉, 〈|y _N − σ₁ y _P ^c |〉 and 〈|y _N ² −σ ₁ ² (y _P ^c )²|〉 (wherey _N andy _P ^c are the normalized structure amplitudes of the structure and the model respectively) are derived in terms of the heavy atom contributionσ ₁ ² for monoclinic and orthorhombic crystals containing a few (i.e., 1 or 2) heavy atoms of the same kind per asymmetric unit by taking the heavy atom part alone as the model. Results are obtained for both the related and unrelated cases. The local values of 〈y _N〉 and 〈|y _N ⁿ − σ ₁ ⁿ (y _P ^c ) ⁿ |〉, (n=1, 2) calculated from these expressions can be used to calculate the overall values of the conventionalR-indicesR(F) andR(I) for the related and unrelated cases. These overall values could be used to check the correctness of heavy atoms located in the structure. Contribution No. 550     

Optical and time-resolved electron paramagnetic resonance studies of the excited states of para-methylcinnamic acid and para-methylcinnamate anion

Time-resolved electron paramagnetic resonance (EPR), fluorescence, and phosphorescence spectra have been observed for the excited states oftrans-p-methylcinnamic acid (p-MeCA) andtrans-p-methylcinnamate anion (p-MeCA^?) in rigid organic glasses at 77 K. With a stretched-polymer-film technique, we assigned the resonance fields in the time-resolved EPR spectra of the lowest excited triplet (T₁) states ofp-MeCA andp-MeCA^?. From the analysis of these spectra we concluded that the deviation from planar structure in the T₁ state is small inp-MeCA andp-MeCA^? and the direction of C=O iss-cis to the ethylenic C=C bond inp-MeCA. The deprotonation appears to have little effect on the zero-field splitting (ZFS) parameters. The ZFS parameters were calculated theoretically using semiempirical molecular orbitals. The sublevel preferentially populated by intersystem crossing (ISC) is T _y in bothp-MeCA andp-MeCA^?. However, following the deprotonation ofp-MeCA, (P _y?P _z)/(P _x?P _z) changes from 5.7 inp-MeCA to 2.1 inp-MeCA^? (P _i are relative populating rates; thex andy axes are close to the long and short in-plane molecular axes, respectively, andz-axis is perpendicular to the molecular plane). The fluorescence lifetimes indicate that the deprotonation has little effect on the sum of the three ISC rate constants for the three T₁ sublevels. A decrease in acidity ofp-MeCA upon excitation has been observed.