EPR study of γ-irradiated three-furancarboxylic acid

The electron paramagnetic resonance of γ-irradiated single crystals of three-furancarboxylic acid has been studied for different orientations of the crystals in a magnetic field. The radicals produced by γ-irradiation have been investigated between 123 and 350 K. The spectra were found to be temperature dependent, and radiation damage centers were attributed to the radical. The principal values of the g-tensor were determined. The results were found to be in good agreement with the existing literature data and theoretical predictions.     

Gamma-radiolysis of deaerated cysteine solutions

The electron paramagnetic resonance (EPR) spectra of gamma-irradiated single crystals of phenidone (fenidon C₉H₁₀N₂O) have been studied for different orientations of crystals in a magnetic field. Phenidone single crystals have been irradiated with ⁶⁰Co-γ rays at room temperature. The EPR spectra have been investigated at temperatures between 125 and 450 K. The spectra have been found to be temperature independent. The spin-Hamiltonian parameters have been obtained from the single-crystal EPR analysis. The principal values of the hyperfine coupling tensor of the unpaired electron and the principal values of the g-tensor have been determined.     

An electron paramagnetic resonance study on irradiated triphenylphosphinselenid single crystal

The single crystals of triphenylphosphinselenid [C₁₈H₁₅PSe] were produced by slow evaporation of concentrated ethyl acetate solutions. These single crystals were exposed to ⁶⁰Co gamma (γ) rays with a dose speed of 0.980 kGy/h at the room temperature for 72 h. The free radical over the sample was observed using electron paramagnetic resonance (EPR)–X band spectrometer. The EPR spectra were recorded between 120 and 400 K. Furthermore, the sample irradiated was rotated in steps of 10° and analyzed for different orientations of the crystal in the magnetic field. Only one radical structure was determined on the molecule. The hyperfine constants of the sample were found to be anisotropic. The average values of these constants and value of g were calculated as following: g=2.007656, a_Se=37.47 G, a_P=27.44 G, a_Ha=17.28 G, and a_Hb=18.16 G.     

Thermoluminescence studies of γ-irradiated nanocrystalline Y3Al5O12

Nanocrystalline yttrium aluminum garnet (Y₃Al₅O₁₂) is synthesized by combustion technique. The X-ray diffraction (XRD) pattern of 900 °C annealed sample revealed a cubic structure. The average crystallite size is found to be 20.5 nm. γ-irradiated Y₃Al₅O₁₂ exhibits two thermoluminescence (TL) glows: a prominent one with a peak at ～410 K and another one with a peak at ～575 K. It is found that the TL glow peak intensity at 410 K increases, while its glow peak temperature is almost steady with an increase in the γ-dose. The effect of the heating rate on the TL glow curve is studied. It is found that T_m1 shifts towards higher temperature region while the I_m1 decreases with an increase in the heating rate. The TL glow curves are analyzed by Chen's peak shape method and the TL parameters are estimated.     

Free radicals in pyrimidines: E.S.R. of a γ-irradiated single crystal of 5-nitrouracil

Free radicals are observed in γ-irradiated single crystals of 5-nitrouracil with the unpaired electron showing hyperfine interaction with one nitrogen atom. The principal values of hyperfine coupling are A_x = 22·5 g, A_y = 25·2 g, and A_z = 40·0 g, and the principal values of the spectroscopic splitting factor are g_u = 2·0117, g_v = 2·0064 and g_w = 2·0027. The relationship of the directions of the corresponding principal axes to the molecular orientations show that the unpaired electron must be located in an sp ² orbital on either N₍₁₎ or N₍₅₎. Considerations of the mechanism of radical formation and comparison to radiation damage in other molecules make the N₍₁₎ location seem more probable. The π interaction of the nitro group on C₍₅₎ evidently prevents the formulation of free radicals with the unpaired electron on C₍₅₎. That carbon atom is the most common location of unpaired electron density in other pyrimidine free radicals.     

Effects induced by 𝛄-irradiation on intraband transitions in Sr2+-doped ammonium zinc chloride crystals

Considerable changes were observed in the X-ray diffraction pattern of ammonium zinc chloride after doping with Sr²⁺ in different concentrations and after irradiating with γ rays at different doses. The effect of γ-radiation and Sr²⁺ content on optical parameters of (NH₄)₂ZnCl₄: x Sr²⁺ single crystals (x?=?0.00, 0.020, 0.039, 0.087 or 0.144?wt.%) has been investigated. The transmittance near the absorption edge of unirradiated crystals and crystals irradiated with different γ-doses has been measured, hence the absorption coefficient (α) was calculated. The values of α at room temperature increased under the influence of γ-irradiation. The rate by which α increases with photon energy just before the absorption edge is strongly inhibited by higher γ-doses. The type of intraband transition in (NH₄)₂ZnCl₄: x Sr²⁺ single crystals was found to be of the allowed indirect transition, and γ-irradiation had no effect on the type of transition. The values of the optical energy gap (E _g ) were calculated as a function of γ-dose. The effect of γ-irradiation was found to be more pronounced on samples doped with x?=?0.087 or 0.144?wt.% Sr²⁺. The results can be discussed on the basis of γ-irradiation-induced defects and Sr²⁺ concentration. A diagram representing probable transitions to the created bands due to irradiation could be constructed.     

Thermo-luminescence kinetic parameters of γ-irradiated Sr4Al14O25:Eu2+, Dy3+ phosphors

In this paper, we present a detailed investigation of the thermo-luminescence (TL) kinetics of the long afterglow phosphor, Sr₄Al₁₄O₂₅:Eu²⁺,Dy³⁺, synthesized by the combustion method. Kinetic parameters such as the activation energy (E_α), the frequency factor (s) and the order of kinetics (b) were calculated using Chen's formulism. The crystalline structure of the phosphor was examined using X-ray powder diffraction and transmission electron microscopy. The average particle size was found to be in the range of 45–52 nm. The optimum dopant concentrations were Eu (1 mol%) and that of Dy (2 mol%). The TL response of the phosphor was monitored after the samples were irradiated with a γ-dose using a ⁶⁰Co source in the 20-800 Gy range. A broad TL peak, (stretching from 328 to 410 K) with a maximum at 368 K was observed. With increasing irradiation dose, the main peak shifts toward higher temperatures. Symmetry factor calculations show that the main TL glow peak obeys second-order kinetics, which could be attributed to the creation of deep level traps. This means that γ-ray irradiation greatly affects the distribution of traps in the Sr₄Al₁₄O₂₅:Eu²⁺,Dy³⁺ phosphor. The phosphor showed a linear response with γ-dose.     

ESR spectroscopics study of radicals formed from methoxycarbonylcholine picrate hemihydrate

Abstract

The electron spin resonance of γ-irradiated single crystals of methoxycarbonylcholine picrate hemihydrate, C₇H₁₆NO₃ ⁺ · C₆H₂N₃O₇ ^? · ½ H₂O has been observed and analyzed for different orientations of the crystal in the magnetic field. The crystals have been investigated between 70 and 350 K. The spectra were found to be temperature independent and the radiation damage centers are attributed to – ?[Obar]OCH₃ and –CH₂CH₂O? radicals. The g and hyperfine coupling constants were found to be almost isotropic with an average, g = 2.0060, a _H1 = 4.4G for –CH₂CH₂O?, g = 2.0050, a _H2 = 3.5G for –CH₂CH₂O? and g = 2.0045, a _H = 3.5 G for –?[Obar]OCH₃. These values indicate a long-range coupling between the unpaired electron and H protons.     

ESR studies of Cl2- (VK) centre trapped in irradiated Ca(ClO3)2 . 2H2O single crystals

A Cl₂- centre has been trapped in X or γ-irradiated Ca(ClO₃)₂. 2H₂O single crystals at 298 K, when the irradiated crystals were illuminated with ultra-violet light (360 nm). This centre is formed at the expense of ClO₂ centres in this crystal. This Cl₂ ^- centre is trapped at two magnetically inequivalent sites in the crystal lattice and these sites become equivalent when the static magnetic field is parallel or perpendicular to the b axis. At many orientations this centre reveals ‘super-hyperfine’ interaction with a proton (I = 1/2) of the water of crystallization. The magnetic parameters are close to those observed in alkali chlorides and the E.S.R. spectrum has been fitted to an orthorhombic spin hamiltonian. The principal g values are g_xx = 2·035, g_yy = 2·033 and g_zz = 2·000 and those of the A values are A_xx = 15·0, A_yy = 31·0 and A_zz = 109·0 G. The shfs parameters are A _‖' = 5·0 A _⊥' = 1·0 G. The V_K centre trapped in this lattice is exceptionally stable at room temperature.     

Phase transition in Cu2+-doped RbH2 PO4 as observed by EPR

The electron paramagnetic resonance (EPR) spectra of Cu²⁺-doped RbH₂ PO₄ at elevated temperatures indicate a phase transition at 358 K. The EPR-silent state at this temperature is attributed to a so-called polymeric phase transition. After the transition when the temperature is lowered to 293 K, the EPR signal does not appear; therefore, the transition is irreversible. This result seems to be in agreement with the other observations. The EPR spectra for the sample indicate the presence of two sites for Cu²⁺, and the values of EPR parameters are in accord with the literature on Cu²⁺-doped single crystals. Any other phase transitions could not to be observed at low temperatures down to 113 K.     

Ab initio study on the high superconducting transition temperature in calcium under high pressure

For calcium in the phases IV and V, we estimated the superconducting transition temperature T _c by the use of the Allen–Dynes formula. Setting the effective screened Coulomb repulsion constant μ* at 0.1 in the formula, we obtained T _c =23.42 K at 100 GPa for Ca-IV and T _c =15.87 K at 120 GPa for Ca-V. In order to clarify the origin of such high values of T _c , first, we investigated the band character of electrons and found that the high T _c is not necessarily related to the so called s–d transfer. Then we analyzed the electron–phonon coupling at each phonon mode in Ca-V where the highest T _c in elements has been experimentally observed. As a result, we discovered that an optical mode at the Γ point has the strongest electron–phonon coupling. Such phonon mode can exist only in the complex crystal structure of Ca-V, and the result shows that the high T _c seems to be closely linked with the complex crystal structures like Ca-IV and Ca-V.     

First-principles study on superconductivity of solid oxygen

The superconductivity of solid oxygen in ζ phase was investigated by first-principles calculations based on the density functional theory. Using a monoclinic C2/m structure, we calculated the superconducting transition temperature by the Allen–Dynes formula and obtained 2.4 K at 100 GPa for the effective screened Coulomb repulsion constant μ* of 0.13. The transition temperature slowly decreases with increasing pressure and becomes 1.3 K at 200 GPa. The phonon analysis shows that the electron–phonon coupling is dominantly enhanced by the intermolecular vibrations of O₂ rather than the intramolecular ones. The phonon modes showing the strong electron–phonon coupling were found to be concentrated in the phonon frequency range of 100–150 cm^?1 at around the M-point in the Brillouin zone.     

Electrical and thermoluminescence properties of γ-irradiated La2CuO4 crystals

Abstract

Measurements of the electrical properties of unirradiated as well as γ-irradiated La₂CuO₄ crystals were carried out at different temperatures in the frequency range of 0.1-100 kHz. Thermoluminescence (TL) studies were also performed on such crystals in the temperature range of 300-600K. The conductivity of the unirradiated La₂CuO₄ crystals were found to obey the power law frequency dependence at each measured temperature below the transition temperature (T_c = 450K). The activation energies for conduction and dielectric relaxation time have been calculated. The TL response and the dc resistance were found to increase with γ-irradiation dose up to 9-10 kGy. The results showed that the ferroelastic domain walls of La₂CuO₄ crystal as well as its TL traps are sensitive to γ-raditaion. This material can be used in radiation measurements in the range 225 Gy-10 kGy.     

Examination of optical properties and estimation of mechanical energies of irradiated polypropylene and teflon

The optical absorption and mechanical yielding energy has been studied under exposure of γ-radiation. Two crystalline polymers, polypropylene (PP) and Teflon, were irradiated with a ⁶⁰Co source, with doses ranging up to 6 kGy. The observed optical energy gap (E _opt) and energy gap tail (Δ E) for irradiated thin sheets of PP were determined from the measured absorption spectra. The average values of (E _opt) and (Δ E) were 5.85 and 0.5 eV, respectively. There is no detectable change in the optical energy gap under the applied γ-ray doses. On the other hand, the effect of γ-radiation on mechanical properties of irradiated Teflon was much pronounced. It was found that Young’s modulus and yield stress increase with radiation dose, whereas the yield strain decreases. The calculated yield energy increases with radiation dose from 0.27 to 0.35 Mpa per unit volume. The enhancement in the mechanical properties of irradiated Teflon was attributed mainly to crosslinking process and other structural changes occuring during irradiation with γ-rays.     

Electroconductivity and pressure–temperature states of step shocked C60 fullerite

A study of electrophysical and thermodynamic properties of C₆₀ single crystals under step shock loading has been carried out. The increase and the following reduction in specific electroconductivity of C₆₀ fullerite single crystals at step shock compression up to pressure 30 GPa have been measured. The equations of state for face centred cubic (fcc) C₆₀ fullerite as well as for two-dimensional polymer C₆₀ and for three-dimensional polymer C₆₀ (3D-C₆₀) were constructed. The pressure–temperature states of C₆₀ fullerite were calculated at step shock compression up to pressure 30 GPa and temperature 550 K. The X-ray diffraction studies of shock-recovered samples reveal a mixture of fcc C₆₀ and a X-ray amorphous component of fullerite C₆₀. The start of the formation of the X-ray amorphous component occurs at a pressure P _m≈ 19.8 GPa and a temperature T _m≈ 520 K. At pressures exceeding P _m and temperatures exceeding T _m, the shock compressed fullerite consist of a two-phase mixture of fcc C₆₀ fullerite and an X-ray amorphous component presumably consisting of the nucleators of polymer 3D-C₆₀ fullerite. The decrease in electroconductivity of fullerite can be explained by the percolation effect caused by the change of pressure, size and number of polymeric phase nuclei.     

X-band EPR study on benzo[c]cinnoline single crystals

The benzo[c]cinnoline compound has been crystallized in ethanol solution. These crystals have been irradiated with ⁶⁰Coγ-rays at room temperature. The crystals have been investigated by an X-band electron spin resonance (ESR) spectrometer two days after irradiation. Very strong ESR peaks have been observed at the temperatures between 130 and 430 K. However, a line broadening has been observed at 130 K. Also analyses found that EPR specra are temperature-dependent and show anisotropic behaviour.     

Low temperature photoconductivity in electron - irradiated p-type Si

The photoconductivity spectra of p-type silicon irradiated at ～15 °K with 1.2 MeV electrons were studied in the wavelength range from 1.2 to 5.5 μ at temperatures from 23 to 80 °K. The 3.9 μ photoconductivity band appears immediately after irradiation in all crystals already at low temperatures, giving further evidence that it is due to the divacancy formed directly during irradiation by electrons. Three main annealing stages of the photoconductivity have been observed; (a) below 160 °K, (b) 160–250 °K, and (c) 280–360 °K. A radiation-induced deep level at E_v , +(0.12±0.02 eV disappears upon annealing at stage b. The annealing behavior of the spectra depends strongly on the measuring temperature. The dependence of the spectra on chopper speed was also investigated.     

Critical magnetic behaviour of triuranium tetraphosphide U3P4

The initial susceptibility and spontaneous magnetization of U₃P₄ single crystals were found to follow the simple power laws, describing by the critical exponents γ, β and δ, whose values were established to be 1.19±0.01, 0.391±0.003 and 4.03±0.05, respectively. The Curie temperature of U₃P₄ determined in different ways is equal to (137.5±0.1) K. The obtained values of the critical exponents are exactly consistent with the scaling relation. In view of the extremely large magnetocrystalline anisotropy present in U₃P₄, the above values are first compared to those of similar anisotropic materials and then discussed in terms of a three dimensional Ising system.     

E.P.R. study of γ-irradiated single crystals of K2C2O4.H2O and (NH4)2C2O4.H2O

The electron paramagnetic resonance of γ-irradiated single crystals of K₂C₂O₄.H₂O and (NH₄)₂C₂O₄.H₂O has been studied. The spectra show interesting microwave power saturation effects. The singlet spectrum is attributed to the C₂O₄ ^- radical derived from the C₂O₄ ^-- ion. The principal g-values are determined to be 1·998, 2·0028 and 2·0004. Certain weak lines are observed with different power saturation and interpreted as due to OH radicals derived from water molecules in the crystal lattice.     

Dissymmetrization in X-irradiated RbTiOPO4 crystal

Electron paramagnetic resonance has been used to study the hole and electron paramagnetic centers formed in X-irradiated RbTiOPO₄, the crystals of the KTP family. X-irradiation of RbTiOPO₄ crystals at 77 K produced an oxygen hole center and four different trivalent titanium electron centers I₁, II, III and IV. Theg-tensors, their principal values and axes for the defects were calculated and compared with those for KTiOPO₄ centers. X-irradiation at 300 K produced another two oxygen hole centers and three electron centers I₁, I₂ and II. EPR spectra of the center II revealed dissymmetrization, i.e., irregular distribution of growth defects, between the physically equivalent sites lowering the point group symmetry of the local environment of paramagnetic centers Ti³⁺.