EPR and Optical Absorption Study of VO2+-Doped Lithium Hydroxylammonium Sulphate

ABSTRACT

Single-crystal and powder EPR studies of VO²⁺-doped lithium hydroxylammonium sulphate (LiNH₃OHSO₄) were carried out at room temperature. The results indicate the presence of two magnetically inequivalent VO²⁺ sites. The VO²⁺ ion takes up a substitutional position in the host lattice. The angular variation of EPR spectra in three mutually perpendicular planes were used to determine the spin Hamiltonian parameters, and the values obtained were the following: For Site 1, g_x = 2.0249 ± 0.0002, g_y = 1.9698 ± 0.0002, g_z = 1.9552 ± 0.0002, A_x = (51 ± 2) × 10^?4 cm^?1, A_y = (93 ± 2) × 10^?4 cm^?1, and A_z = (165 ± 2) × 10^?4 cm^?1; and for Site 2, g_x = 2.0267 ± 0.0002, g_y = 1.9743 ± 0.0002, g_z = 1.9213 ± 0.0002, A_x = (40 ± 2) × 10^?4 cm^?1, A_y = (80 ± 2) × 10^?4 cm^?1, and A_z = (155 ± 2) × 10^?4 cm^?1. The optical absorption spectrum recorded at room temperature shows four bands. From the optical and EPR data, various molecular coefficients are evaluated, and the nature of bonding in the crystal is discussed.     

Electron-Impact Fragmentographic Fluorescence Spectroscopy of Ethanol,Acetaldehyde, 1- and 2-Propanol and Acetone

Abstract

Gaseous ethanol, acetaldehyde, 1-propanol, 2-propanol and acetone at pressures of 2 × 10^?5 to 5 × 10^?4 torr were irradiated with electrons of energies 0-1000 eV. The visible-region fluorescence of the excited fragments was then measured. Studies included pressure dependence, electron energy dependence, threshold energy measurements, and excitation curve measurements. The aim of the research was to ascertain if molecules of similar structure could be differentiated by their spectra.     

Low temperature vibrational relaxation of OD in the A2Σ, state

The vibrational relaxation of the A ²Σ state of OD has been studied in the low translational temperature environment of an argon free-jet (T_trans near 5 K). Using laser induced fluorescence (LIF), the absolute vibrational relaxation rate coefficients were measured for OD A²Σ (ν′) to be 7.1 ± 2.6 × 10^?11, 5.9 ± 1.4 × 10^?11, and 2.7 ± 1.1 × 10^?11 cm³ s^?1 for the ν = 3, 2 and 1 states, respectively. State-to-state relaxation rate coefficients were also obtained for the ν= 1, ? = 1 level going to ν= 0, ? levels in the A²Σ manifold. The rotational relaxation rate coefficient for ν= 1, ?= 1 in the A state of OD was found to be 9.6 ± 1.0 × 10^?11cm³s^?1. These values are consistent with values measured for OH A²Σ, and the total loss rates are near the capture rate coefficient value. The vibrational relaxation rate coefficients k_ν appear to be governed by the vibrational energy of the molecule rather then by interaction with nearby dissociative states such as the a⁴Σ state. The relative Einstein A factors for the A²σ (ν = 3) state of OD were determined and compared with the available calculated value.     

Special Report: High-Speed Access Report—Third Quarter 2010

Abstract

We fabricated Bragg gratings in planar lightwave circuits and investigated their growth characteristics. The refractive index modulation of the gratings grew in the PLC with total fluence F by the power law δ n = AF ^B with A = 8.6 ± 0.9 × 10^?8 and B = 1.47 ± 0.02. The PLC gratings as external reflectors for ECLs were controlled reasonably well by adjusting the writing conditions based on the power law and the coupled mode theory. The properties of fabricated PLC gratings were closely matched to the design parameters of the PLC grating. The single longitudinal mode oscillations of the ECLs were also demonstrated at 1309.5 nm and 1550.5 nm.     

Radiation enhanced diffusion in UO2 and (U,Pu)O2

Abstract

The radiation enhanced diffusion (coefficient D*) of U-233 and Pu-238 in UO₂ and (U, Pu)O₂ with 2.5 and 15% Pu was measured during fission in a nuclear reactor. Normal diffusion sandwiches with a thin tracer layer were used. A radio-frequency furnace allowed the temperatures to be varied between 130 and 1400°. Neutron fluxes (7 × 10¹² to 1.2 × 10¹⁴ n cm^?2 s^?1) and irradiation times (56 to 334 h) were also varied to cover ranges of fission rates [Fdot] between 7× 10¹¹ and 6.4 × 10¹³ f cm^?3 s^?1 and of doses F between 4.2 × 10¹⁷ and 3.1 × 10¹⁹ f cm³. Below ～1000°, D* was completely athermal and increased linearly with [Fdot]. It was described by D* = A[Fdot] with A = 1.2× 10^?29cm⁵. A possible temperature dependence was indicated between ～1000and 1200°. The results are explained in terms of thermal and pressure effects of fission spikes and are related with other studies of radiation damage as well as with technologically interesting processes occurring in UO₂ during irradiation.     

EPR of Cu2+ Impurities in Cytosine Hydrochloride: A Case of Superhyperfine Structure

Electron paramagnetic resonance spectra of Cu²⁺ impurities in cytosine hydrochloride single crystals are observed at liquid nitrogen temperature. Two magnetically equivalent sites for Cu²⁺ have been observed. The parameters of ⁶³Cu obtained with the fitting of spectra to rhombic symmetry spin Hamiltonian are: g _x  = 2.047 ± 0.002, g _y  = 2.187 ± 0.002, g _z  = 2.390 ± 0.002, A _x  = (86 ± 3) × 10^?4 cm^?1, A _y  = (87 ± 3) × 10^?4 cm^?1, and A _z  = (138 ± 3) × 10^?4 cm^?1. The observed bands in optical spectra of the single crystal recorded at room temperature are assigned to various d–d and charge-transfer transitions. Using both EPR and optical data, the nature of bonding of metal ion with different ligands is discussed.     

Measurement of Ar(I) and Ar(II) transition probabilities in LTE ARC plasmas

The transition probabilities of two Ar(I) lines and one Ar(II) line have been measured in emission on wall-stabilized argon arc plasmas (0·5×10⁵?p, Nm^-2?3×10⁵; 10,000?T, K?20,000; 10²²?N_e, m^-3?5×10²³) using the “method of best fit (MBF)”. The results (without line-wing correction) are for Ar(I) at 714·7 nm, A_nm=5·66×10⁵ s^-1±5%; for Ar(I) at 430·0 nm, A_nm=3·40×10⁵ s^-1±5%; for Ar(II) at 480·6 nm, A_nm=8·82×10⁷ s^-1±7%. These values were not influenced by deviations from LTE, which have been observed at electron number densities n_e?10²³ m^-3. The small uncertainties were achieved after careful corrections of different sources of error.     

The average structure of 5.10-Dihydro-5.10-Diethylphenazinium-Iodide (E2P·I1.6): A new linear chain Polyiodide compound

Upon oxidation of 5.10-dihydro-5.10-diethylphenazine (E₂P) with iodine golden-green lustrous crystals of a compound with stoichiometry E₂P.I_1.6 were isolated. The compound crystallizes in the tetragonal space group D₄² with $\text{a = 12.321(2)}\text{A}\text{?}$ and $\text{c = 5.330(2)}\text{A}\text{?}$. The E₂P and I form interpenetrating incommensurate sublattices along c, with an iodine repeat distance of 9.7 Å. Static susceptibility measurements at room temperature give χ_g = + 0.994 × 10^?6g^?1 × cm³. This corresponds to one unpaired electron spin per two formular units. Single-crystal EPR indicates that the paramagnetism is associated with weakly interacting E₂P⁺ cation radicals. The 300K-d.c. conductivity of 3×10^?2Ω^?1cm^?1 and activation energy of 0.17±0.02eV for single crystals is consequently associated with the polyiodide chains, and not with the E₂P⁺ cation radicals.     

A Study on the Permeability of the Triton X-100 Micelles by Fluorescence Decay Kinetics of Probe Molecules

Abstract

The third armonic (355 nm) of a pulsed Nd-YAG laser has been used to excite pyrene in micellar solutions of Triton X-100. Fluorescence quenching by nitromethane and triethylamine of the excited state of pyrene in Triton X-100 has been studied. Quenching rate constant values of 4.94 ± 0.13 × 10⁸M^?1s^?1 and 1.50 ± 0.04 × 10⁸M^?1s^?1 for deactivation by nitromethane and triethylamine, respectively, have been measured. The values obtained are discussed in terms of the interface permeability.     

Excitation of 3−1, 5−1 and 7−1 states in Te isotopes A = 120, 122; 124, 126, 128 WITH (p,t) reactions

The reactions ^ATe(p, t)^A?2Te have been studied with even-A targets using 51.9 MeV protons. Three or more strongly excited triton peaks were observed in the spectra of the ^A-2Te nuclei at energies of ≈ 2–3 MeV excitation. Angular distributions are analyzed using DWBA theory. The lowest octupole (3^?₁) states of five Te isotopes are strongly excited. The lowest 3^? state in ¹²⁰Te is established at 2.09 ±0.02 MeV. The systematics of excitation energies and cross sections for the lowest 5^? and 7^? states are interpreted by a quasiparticle model.     

Annealing of arsenic-and antimony-implanted silicon single crystals using A CW xenon arc lamp

Abstract

Continuous, incoherent light from a xenon arc lamp has been used to anneal radiation damage in <100> silicon single crystals produced by implantation of 30?keV arsenic or antimony ions to doses between 1×10¹⁵ cm^?2 and 1×10¹⁶ cm^?2. The recrystallized layers have been characterized by Rutherford-backscattering spectroscopy, ion-channeling, Transmission Electron Microscopy, and sheet-resistivity measurements.     

ESR of V3+ in zinc oxide single crystals

Electron spin resonance has been investigated in zinc oxide single crystals containing vanadium. Several groups of ordinary and forbidden transitions can be observed. The experimental results are interpreted with the aid of the spin Hamiltonian, for which the following parameters were determined:g∥=1.945; ⊥=1.937; ¦D¦=750×10^?4 cm^?1, ¦A¦=68 × 10^?4 cm^?1; ¦B ¦=93×10^?4 cm^?1; ¦A?P¦=65×10^?4cm^?1.     

Pressure balance used as standard in the pressure range 0.1 to 1 Gpa

Abstract

To complete his celibration facilities in the ranae 10 kPa to 200 MPa, L. N. E. has developed a new pressure balance in the range 30 - 1 000 MPa. This balance wzs especielly lecicned in order to determine the pressure distortion coefficients of the piston-cylinder essenblies. The uncerteinty of this standard was estimated to be ± 20×10^?6 at 100 Mpa and ±90×10^?6at 1 000 MPa.     

ESR and optical study of Cu2+-doped bis-(5,5′-diethylbarbiturato)bis picoline Zn(II)

ESR studies were conducted on Cu²⁺-doped bis-(5,5′-diethylbarbiturato)bis picoline Zn(II). Two Cu²⁺ lattice sites, Cu²⁺(I) and Cu²⁺(II), were identified. These sites exhibit two sets of four hyperfine lines in all directions. The g factor and hyperfine splitting were calculated from ESR absorption spectra: g_x ?=?2.0201?±?0.002, g_y ?=?2.0900?±?0.002, g_z ?=?2.1634?±?0.002, A_x ?=?(30?±?2)?×?10^?4?cm^?1, A_y ?=?(40?±?2)?×?10^?4?cm^?1 and A_z ?=?(154?±?2)?×?10^?4?cm^?1. It was found that Cu²⁺ enters the lattice substitutionally. The ground-state wavefunction of the Cu²⁺ ion in this lattice was determined from the spin Hamiltonian constants obtained from the ESR studies. With the help of an optical absorption study, the nature of the bonding in the complex is also discussed.     

Spectroscopic study of thulium-activated double sodium yttrium fluoride Na<Subscript>0.4</Subscript>Y<Subscript>0.6</Subscript>F<Subscript>2.2</Subscript>:Tm<Superscript>3+</Superscript> crystals: I. Intensity of spectra and luminescence kinetics

Na_0.4Y_0.6F_2.2:Tm³⁺ crystals with a thulium content from 1 to 100 at % have been grown by the Stockbarger-Bridgman method. The optical spectra of Na_0.4Y_0.6F_2.2:Tm³⁺ crystals were investigated in detail at room and low (10 K) temperatures, and the luminescence kinetics was analyzed using different excitation methods. The structure of the Stark splitting of thulium levels as “quasi-centers,” characterized by inhomogeneous broadening of the Stark components, is determined from analysis of the absorption spectrum at 10 K. The oscillator strengths of the transitions from the ground state to excited multiplets are determined from the absorption cross-section spectra at 300 K for ten transitions in the range 5000–38 500 cm^?1 and seven transitions in the range 5000–28 500 cm^?1. The transition intensity parameters Ω _t , obtained by the Judd-Ofelt method from the spectra due to the transitions to ten and seven excited levels, were found to be, respectively, (i) Ω₂ = 1.89 × 10^?20, Ω₄ = 2.16 × 10^?20, and Ω₆ = 1.40 × 10^?20 cm² and (ii) Ω₂ = 2.04 × 10^?20, Ω₄ = 2.01 × 10^?20, and Ω₆ = 1.44 × 10^?20 cm². These values of the intensity parameters were used to calculate the radiative transition probabilities and branching ratios and to estimate the multiphonon nonradiative transition probabilities for NYF:Tm. The luminescence decay kinetics from thulium radiative levels upon their selective excitation by nanosecond laser pulses has been studied and the lifetimes of thulium radiative levels in NYF crystals have been found.     

Bound Energy of Water in Hard Dental Tissues

Abstract

Enamel and dentin are composed, respectively, of 3 wt% and 10 wt% of water, which exhibits different features in the tissues: loosely and tightly bound water. The objective of this study is to clarify by infrared spectroscopy, the different features of the water in heated (100–1000°C) hard dental tissues (enamel and dentin). The water band between 3800 cm^?1 and 2500 cm^?1 was analyzed by infrared spectroscopy. The area dependence of the water band with temperature was compared with the Arrhenius equation in two regions (100–400°C and 700–1000°C). The activation energy was determined for these two regions, and similar values were observed for both tissues. For enamel we obtain ?4.1±0.2 kJ/mol at 100–400 °C and ?63±9 kJ/mol at 700–1000°C; for dentin ?4.1±0.2 kJ/mol at 100–400°C and ?60±11 kJ/mol at 700–1000°C. The water loss changes the color of the tissues, hydroxyapatite crystallographic parameters, and produce ESR signals. These changes were discussed and compared with the results observed in this work and after laser irradiation. We conclude that these two activation energies could be assigned to the adsorbed (loosely bound) and trapped (tightly bound) water.     

Growth and characterization of L-phenylalanine nitric acid (LPN) and tris L-(phenylalanine)-phenylalanininum nitrate (TPLPN) as second and third order nonlinear optical materials

We synthesized noncentrosymmetric single crystals of L-phenylalanine nitrate (LPN) and tris L-(phenylalanine) L-phenylalaninium nitrate (TPLPN) by slow solvent evaporation technique. Both crystallized in monoclinic system with different acentric space groups namely P2₁ (LPN) and C2 (TPLPN) respectively. The IR and Raman spectral investigation was done for LPN and TPLPN and discussed. The UV-vis-studies accomplished the excitation wavelength of the grown crystals suitable to exhibit second harmonic generation signal. From the absorption data, remarkable optical properties such as direct band gap energy, Urbach energy, extinction coefficient were evaluated. The mechanical strength of the grown crystal was examined by Vickers micro hardness test. The temperature of decomposition was confirmed by TG/DSC analysis. Fluorescence emission spectrum of LPN and TPLPN were recorded and lifetime was also studied. The dielectric constant and dielectric loss of LPN and TPLPN has been determined as a function of frequency and temperature. Also the surface topologies of the crystallized salts were assessed by SEM studies. The third-order nonlinearities of LPN and TPLPN were determined by Z-scan technique with Nd: YAG at 532?nm and thereby from closed and open Z-scan data, third-order susceptibilities were calculated to be χ⁽³⁾?=?8.826?×?10^?6 esu for LPN and χ⁽³⁾?=?2.552?×?10^?7 esu for TPLPN.     

Growth of high quality non-linear optical crystal zinc germanium phosphide for Mid-infrared optical parametric oscillator

ZnGeP₂ single crystals were grown from Vertical Bridgman method. High-quality near-stoichiometric ZnGeP₂ single crystals were obtained in the diameter of 30 mm and length of 120 mm. The results showed that after thermal annealing of the crystals the optical absorption coefficient was below 0.03 cm^?1 at 2.05 μm, and ～0.02 cm^?1 at 3–8 μm. The low absorption loss ZnGeP₂ samples with dimension of 6 × 6 × 18 mm³ were cut from the annealed ingots for 3–5 μm optical parametric oscillation (OPO) experiments. For OPO experiment, we obtained up to 8.7 W output in the 3–5 μm wavelength range (with signal of 3.80 μm and idler of 4.45 μm, respectively) pumped by a 16.3 W 2.05 μm Tm,Ho:GdVO₄ laser at pulse repetition rate of 10 kHz, which corresponded to a conversion efficiency of 53.4% and slope efficiency of 64.8%, respectively.     

Laser Induced Energy Transfer Studies in Polyatomic Mixtures: CH3F-NO2

Abstract

The internal kinetics of NO₂ as well as the kinetics of crossover between CH₃F and NO₃ were studied in mixtures of these polyatomics and rare gases.

Subsequent to excitation of the CH₃F to v ₃=1 by the P(20) line of a 9.6μ Q-switch CO₂ laser, fluorescence of NO₂ at 6.12μ from v ₃=1 was monitored.

The equilibration rate of the stretching modes in NO₂ was determined to be 46 ± 10 msec^?1 torr^?1 while the rate of stretches-bend equilibration was measured as 15 ± 3 msec^?1 torr^?1. The rate of crossover from excited CH₃F to NO₂ in high rare gas dilution was measured as 90 ± 20 msec^?1 torr^?1 and the reverse rate as 285 ± 60 msec^?1 torr^?1.

Comparison to other triatomic systems as well as other experiments with mixtures of polyatomics are made and implications of laser “photochemistry” of NO₂ reactions are discussed.     

Absorption of Dy3+ and Nd3+ ions in BaR 2F8 single crystals

The Dy³⁺ absorption and excitation spectra of BaY₂F₈ and BaYb₂F₈ single crystals are investigated in the ultraviolet, vacuum ultraviolet, and visible ranges at a temperature of 300 K. These crystals exhibit intense broad absorption bands due to the spin-allowed 4f-5d transitions in the range (56–78) × 10^?3 cm^?1 and less intense absorption bands that correspond to the spin-forbidden transitions in the range (50–56) × 10^?3 cm^?1. The Nd³⁺ absorption spectra of BaY₂F₈ single crystals are studied in the range (34–82) × 10^?3 cm^?1 at 300 K for different crystal orientations.