EPR spectrum of donors in 6H SiC in a broad temperature range

An EPR study of donors in 6H SiC crystals with an uncompensated donor concentration (N _D−N _A) of 2×10¹⁸ to 1×10¹⁶ cm⁻³ performed in the temperature range 4.2 to 160 K at frequencies of 9 and 140 GHz showed that 6H n-SiC samples have two donor states in the gap. One of them originates from nitrogen occupying three inequivalent lattice sites with ionization energies of 150 and 80 meV, and the second is connected with a structural defect lying deeper in the gap than nitrogen. The temperature dependences of donor EPR line intensities have been found to deviate from the Curie law. The observed EPR line-intensity peaks of donors are produced in a temperature-driven successive redistribution of donor electrons between the donor levels. The temperature dependences of EPR line intensities obtained from samples with low donor concentrations were used to determine the valley-orbit splitting of nitrogen in cubic sites. Fiz. Tverd. Tela (St. Petersburg) 40, 1824–1828 (October 1998)     

Line positions and intensities of acetylene in the 2.2-μm region

More than 440 line positions and intensities of 8 bands of acetylene are measured in the 2.2-μm spectral region. A multispectrum fitting procedure has been applied to retrieve line parameters. The average absolute accuracy of the line parameters obtained in this work is estimated to be ±0.0005 cm⁻¹ for the line positions, and ±5% for the line intensities. Vibrational transition dipole moment and Herman-Wallis coefficients are determined for two of the studied bands. An unusual rotational dependence of the vibrational-rotational transition dipole moment of remaining bands has been found. All measured line intensities are treated simultaneously within the framework of the effective operators approach. The sets of effective dipole moment parameters obtained reproduce the observed line intensities within the experimental uncertainty.     

EPR Spectra of Nitrogen in Ultra-Dispersed Diamonds

The analysis of the electron paramagnetic resonance (EPR) line shape of ultra-dispersed diamond (UDD) obtained by conversion of trotyl and hexogen mixture and purified from other phases and metal compounds is carried out. The observed wide line with g = 2.0028 and a line width of 8.7 G is shown to be formed by superposition of three lines with line widths of 15.3, 8.5 and 3 G and with a ratio of integral intensities of 70:30:1. The procedure of decomposition and subtraction of wide lines has revealed the resolved hyperfine structure (HFS) from donor nitrogen with parameters A = 40.8 G and B = 29.2 G. Experimentally obtained dependence of the line width of the exchange line on the concentration of donor nitrogen in synthetic diamonds assumed that variations in line widths of the EPR spectrum components are caused by different local concentration of donor nitrogen due to distribution of nitrogen impurity during crystallization of diamond nanoparticles. EPR spectra of UDD after annealing in vacuum and at high pressures in the range of diamond phase stability are also discussed. At high-pressure annealing above 973 K, the areas with high concentration of defects are graphitized and a narrow Dyson-shape line from conductivity electrons and a resolved HFS from donor nitrogen can be observed without additional treatment of the EPR spectrum.     

Line intensities in the 1.5-μm spectral region of acetylene

Line intensities are measured for 546 transitions belonging to 13 bands of the main isotopologue ¹²C₂H₂ of the acetylene molecule, in the 1.5-μm spectral domain. A multispectrum fitting procedure is used to retrieve line parameters from Fourier transform spectra. Prior to this work, line intensities were known for only 4 bands in this spectral region, from the work of El Hachtouki and Vander Auwera [Absolute line intensities in acetylene: the 1.5 μm region. J Mol Spectrosc 2002;216:355-62]. An excellent agreement is found with the results of these authors, showing that the accuracy of both results is likely better than 1% for the strong bands. However, the spectrum becomes very crowded when one wants to study weaker bands, so that the average accuracy of the intensities reported in the present work is 5%. From these data, vibrational transition dipole moments squared and Herman-Wallis coefficients have been determined for all the bands.     

Electron paramagnetic resonance in a Gd<Subscript>0.14</Subscript>Si<Subscript>0.86</Subscript> amorphous film: Bottleneck regime

Electron paramagnetic resonance (EPR) in a Gd_0.14Si_0.86 amorphous film is studied over a wide temperature range from 4 to 300 K. The experimental results are analyzed with regard to the strong structural disorder in the system under study. This disorder leads to the formation of droplets, that is, regions with a high density of electronic states. It is shown that the observed EPR signal can be formed only in the double bottleneck regime, and temperature dependences are obtained for the line position and width. The spin-lattice relaxation rates for electrons and Gd ions, the second spectral moment of the line, the ferromagnetic transition temperature, the number of Gd atoms in the droplets, and the product of the electron density of states by the exchange coupling constant between electrons and Gd ions are evaluated from comparison with experimental data. The values obtained corroborate the validity of the assumptions that the double bottleneck conditions are fulfilled and structural and phase nanoscale inhomogeneities exist in the system.     

Absolute line intensities measurements and calculations for the 5.7 and 3.6 μm bands of formaldehyde

The goal of this study is to achieve absolute line intensities for the strong 5.7 and 3.6 μm bands of formaldehyde and to generate, for both spectral regions, an accurate list of line positions and intensities. Both bands are now used for the infrared measurements of this molecule in the atmosphere. However, in the common access spectroscopic databases there exists, up to now, no line parameters for the 5.7 μm region, while, at 3.6 μm, the quality of the line parameters is quite unsatisfactory. High-resolution Fourier transform spectra were recorded for the whole 1600–3200 cm^?1 spectral range and for different path-length-pressure products conditions. Using these spectra, a large set of H₂CO individual line intensities was measured simultaneously in both the 5.7 and 3.6 μm spectral regions. From this set of experimental line strength which involve, at 5.7 μm the ν₂ band and, at 3.6 μm, the ν₁ and ν₅ bands together with nine dark bands, it has been possible to derive a consistent set of line intensity parameters for both the 5.7 and 3.6 μm spectral regions. These parameters were used to generate a line list in both regions. For this task, we used the line positions generated in [Margulés L, Perrin A, Janeckovà R, Bailleux S, Endres CP, Giesen TF, et al. Can J Phys, accepted] and [Perrin A, Valentin A, Daumont L, J Mol Struct 2006;780–782:28–42] for the 5.7 and 3.6 μm, respectively. The calculated band intensities derived for the 5.7 and 3.6 μm bands are in excellent agreement with the values achieved recently by medium resolution band intensity measurements. It has to be mentioned that intensities in the 3.6 μm achieved in this work are on the average about 28% stronger than those quoted in the HITRAN or GEISA databases. Finally, at 3.6 μm the quality of the intensities was significantly improved even on the relative scale, as compared to our previous study performed in 2006.     

EPR study of coke formed on alumina

This study was aimed at characterizing paramagnetic properties of cokes formed on aluminas of different origin (calcined at 400 and 800°C) during catalytic reactions of hexafluoro-2-propanol decomposition and, for the sake of comparison, 2-propanol decomposition at 300 and 400°C. No significant differences in coke-forming activities were found between alumina obtained by hydrolysis of aluminium isopropoxide and that prepared by precipitation with ammonia from aluminium sulfate solution at pH 6.1, although they differed substantially in their acidity patterns. On the other hand, clear differences were observed between intensities of electron paramagnetic resonance (EPR) spectra recorded for samples covered with coke produced by reactions of the two alcohols. When hexafluoro-2-propanol was the parent substance, spectral lines were stronger and narrower than those obtained for 2-propanol. The smaller linewidth (ΔB _pp=0.29-0.54 mT compared to ΔB _pp=0.51-0.92 mT) was most likely a result of exchange interactions between electrons of paramagnetic centers, whose concentrations were higher in the carbonaceous deposit formed from fluorine-containing alcohol. Higher temperature of coke formation (400°C) resulted in higher intensities of EPR spectra, whereas higher temperature of alumina calcination (800°C), prior to its use in alcohol decomposition reaction, brought about lower spectral intensities.     

Optical absorption, EPR, infrared and Raman spectral studies of clinochlore mineral

Optical absorption, EPR, Infrared and Raman spectral studies have been carried out on natural clinochlore mineral. The optical absorption spectrum exhibits bands characteristic of Fe²⁺ and Fe³⁺ ions. A band observed in the NIR region is attributed to an intervalence charge transfer (Fe²⁺-Fe³⁺) band. The room temperature EPR spectrum of single crystal of clinochlore mineral reveals the dominance of Fe³⁺ ion exhibiting resonance signals at g=2.66; 3.68 and 4.31 besides one isotropic resonance signal at g=2.0. The EPR studies have been carried out for a polycrystalline sample in the temperature range from 103 to 443 K and for a single crystal of clinochlore mineral in the temperature range 123-297 K. The number of spins (N) participating in resonance at g=4.3 signal of the single crystal of clinochlore mineral has been calculated at different temperatures. The paramagnetic susceptibility (χ) is calculated from the EPR data at different temperatures for single crystal of clinochlore mineral. The Curie constant and Curie temperature values are evaluated from 1/χ versus T graph. The infrared spectral studies reveal the formation of Fe³⁺-OH complexes due to the presence of higher amount of iron in this mineral. The Raman spectrum exhibits bands characteristic of Si-O-Si stretching and Si-O bending modes.     

Absolute line intensity measurements in the ν2 bands of HDO and D2O using a tunable diode laser spectrometer

Absolute line intensities for several individual vibration-rotation transitions in the ν₂ bands of HDO and D₂O have been determined at room temperature from laboratory spectra recorded with a tunable diode laser spectrometer. Two tunable semiconductor diode lasers operating in the 1250- to 1350- and 1060- to 1140-cm⁻¹ spectral regions have been used in the recording of the data. Comparisons are made with previously published results where appropriate.     

EPR of radiation defects in LiBaF 3 crystals

EPR spectra of LiBaF 3 crystals have been investigated after X-irradiation at RT. A spectrum consisting of approximately 35 nearly equidistant EPR lines has a strong angular dependence on the line intensities. The spectrum is caused by a hyperfine interaction (hfs) of a spin S =1/2 with neighbouring groups of nuclei. The observed large number of hfs lines required Li nuclei being in the first shell and fluorine nuclei in the more distant second shell. We analysed the spectrum in the F -centre model, taking reduced hfs values of the F -centre in LiF and found qualitative explanation of the number of hfs lines. The angular dependence of the line intensities could be explained by an anisotropy of the g -tensor with its main axis along the [1 v 0 v 0] axis of the crystal.     

Effective dipole moment parameters of C2H2 for the 100, 7.7, 1.4, 1.3, 1.2 and 1.0 μm regions

Based on new line intensity measurements collected from the literature, the effective dipole moment parameters of acetylene have been found for the 100, 7.7, 1.4, 1.3, 1.2 and 1 μm spectral regions by least-squares fittings. On average, the experimental uncertainty was obtained in all fits. The new sets of the effective dipole moment parameters combined with those that were previously published allow for the calculation of the line intensities for the majority of the acetylene bands in the spectral range from 100 to 1 μm.     

Anisotropy of phosphorous electron donor state in strained clusters in silicon at low temperatures

An anisotropic EPR spectrum at T = 4 K was observed in silicon samples irradiated by phosphorus ions and subsequently annealed at 1000°C. Epitaxial silicon layers with a natural isotope composition and enriched by ²⁸Si isotope grown on a natural silicon wafer were investigated. The spectrum consisted of three lines corresponding to different g-factor components: g _x ,g _y , and g _z . The central line was overlapped by the isotropic line coinciding by its g-factor with the line of the conduction electrons in silicon. The shape of the spectral lines indicated that the spectrum was due to the paramagnetic centers which belong to the randomly oriented clusters with the anisotropic g-factor. The nature of the anisotropic EPR spectrum is due to the electrons localized on donors located in the strained phosphorous clusters. The strains were caused by either incompletely annealed defects after the phosphorous implantation (E = 40 keV, D = 2 × 10¹⁴ cm⁻², T _ann = 1000°C, 1 h) or phosphorous atoms in clusters. The distance between the components strongly depended on the temperature and microwave power and decreased as they increased.     

Line Intensities of (12)C(16)O(2) in the 1.2-1.4 µm Spectral Region

The 7000-8500 cm(-1) spectral region of (12)C(16)O(2) has been investigated using the high-resolution FT spectrometer of LPPM in Orsay. The two strongest bands in this region are the 10031 <-- 00001 and 10032 <-- 00001 bands centered at 8294 and 8192 cm(-1). Line intensities in these two bands and in the 40013 <-- 00001 and 40014 <-- 00001 bands have been measured. Using the method of effective operators, these line intensities have been included in a new fit of effective dipole-moment parameters to all available experimental data in the same spectral region of (12)C(16)O(2). The corresponding calculated line intensities of the 10031 <-- 00001 and 10032 <-- 00001 bands are compared with the experimental ones. Copyright 2000 Academic Press.     

Effect of annealing on the spin density of dangling bonds and the structures of amorphous germanium

Electron paramagnetic resonance was used to study the dependence of the volume spin density of dangling bonds ina-Ge films produced by cathode sputtering in argon on annealing temperature. The structure of the films is determined by x-ray diffraction analysis. Two EPR lines with g=2.019 and g=2.003 are observed whose intensities change nonmonotonically with annealing temperature. The g=2.019 line is characteristic only of the amorphous state of germanium, while the g=2.003 line persists even after crystallization of the films. When the results are compared with structure data, the conclusion may be drawn that the observed lines in the EPR spectrum are related to the dangling bonds in the peripheral regions of two types of clusters. The g=2.003 line is due to dangling bonds in the peripheral region of clusters with the usual cubic packing of atoms, and the g=2.019 line is due to clusters of the hexagonal type, which is not characteristic of the normal structure of crystalline germanium.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 7, pp. 51–57, July, 1989.     

Spectroscopic Studies on Threonine Doped Polyaniline Composites

The structural and magnetic properties of polyaniline (PANI)- and threonine (T)-doped polyaniline composites were characterized by using FTIR, UV-Vis, and electron paramagnetic resonance (EPR) spectroscopic techniques. The FTIR, UV-Vis, and X-band EPR spectra were recorded for PANI- and threonine-doped polyaniline (PANI-T) composites. The increased intensity of the IR bands in PANI-T composites is due to the increasing dopant concentration. The observed red shift corresponding to the N-H ··· N mode indicates the hydrogen bond formation in between the PANI and threonine molecule. The observed decrease in spectral intensity of the UV-Vis spectrum of the PANI-T composite confirms the occurrence of the protonation at the imine nitrogen sites. The EPR parameters such as line width, g factor, line asymmetry parameter, signal intensity, and spin concentration values were estimated. The EPR spectrum of PANI clearly indicates the presence of unpaired polaron. The EPR signal intensity and spin concentration values decrease with increasing dopant concentration, which reveals the polaron to bipolaron formation in PANI-T composites. EPR lineshape analysis showed that the absorption profile was Gaussian shape. The Gaussian-shaped line is generally due to the dipole–dipole interactions in the PANI and PANI-T composites. The line asymmetry parameter and g values indicated the isotropic nature of PANI and PANI-T composites.     

Theoretical interpretation of spectral signs of an oxymethyl group in the IR spectrum of methyl-β-D-glucopyranoside

For the first time, we have assigned the observed absorption bands and interpreted the IR spectrum of methyl-β-D-glucopyranoside in detail in the 1500–800 cm⁻¹ region, based on a full calculation of the frequencies and absolute intensities of the normal vibrations of the molecule and their comparison with the experimental data. We have identified two groups of spectral signs indicating an oxymethyl substituent has replaced the hydroxyl group on the C₍₁₎ atom in the glucopyranoside: absorption bands of medium intensity due to the characteristic vibrations of the substituent, and intense bands due to an unusual “interaction” between many structural moieties. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 6, pp. 721–727, November–December, 2006.     

Observation of MeV ions in long-pulse, large-scale laser-produced plasmas

A new approach for investigation of the generation of fast ions and hot electrons inside the same plasma volume in laser-produced plasmas is proposed. It is based on the spectroscopic observation of line radiation from singly and doubly excited levels with simultaneous high spectral and spatial resolution. The experimental results demonstrate the observation of fast ions from highly charged target material inside the plasma volume and suggest that the generally accepted scaling relations are seriously invalid under certain conditions. Even at rather modest intensities ions with energies of several MeV are observed. Pis’ma Zh. éksp. Teor. Fiz. 70, No. 4, 262–267 (25 August 1999) Published in English in the original Russian journal. Edited by Steve Torstveit.     

EPR studies of15N- and2H-substituted pH-sensitive spin probes of imidazoline and imidazolidine types

The isotopically substituted analogs of pH-sensitive imidazoline and imidazolidine radicals have been synthesized and investigated with electron paramagnetic resonance (EPR) spectroscopy. The introduction of²H and¹⁵N into the structure of the radical is a useful approach to enhance the information obtained from spin-labeling experiments. The spectra of the radicals have been analyzed with 9.8 (X-band) and 130 GHz (D-band) EPR spectroscopy. The substitution of¹H for²H leads to significant narrowing of Gaussian line width, while the substitution of¹⁴N for¹⁵N in the nitroxyl fragment decreases both the number of spectral lines and Lorentzian line width. These effects result in a significant increase in the peak intensities up to 5–7 times for X-band EPR spectra of one of the imidazoline radicals (R4). The increase in spectral resolution allowed us to reveal the hyperfine interaction splitting with the attached proton (0.36 G) in the protonated form of the radical R4. The influence of proton exchange of the radicals with phosphate and acetate buffers on their EPR spectra has been studied in H₂O and D₂O. The corresponding rate constants of the proton exchange have been calculated from fitting of the simulated EPR spectra line shapes to experimental spectra. The data obtained demonstrated the advantages of the isotopically substituted spin pH probes in spectral resolution and sensitivity which can be an important factor particularly for applications in vivo where the fundamental sensitivity is much lower. The sensitivity of EPR spectra of these spin probes to the buffer capacity could be of practical importance taking into account the biological relevance of monitoring this parameter in some pathological states.     

Lattice damage and Al-metal precipitation in 2.5 MeV-electron-irradiated AlH3

AlH₃ powder was bombarded with energetic electrons at 20 K and at room temperature and investigated by EPR, NMR, X-ray diffractometry, and microwave dielectric-constant measurements. The EPR spectra of the irradiated powder and of a selected single crystal cuboid of mm edge show a complex asymmetric line centered at g = 2.009, with a Curie-like temperature dependence, attributed to radiation-induced color centers and/or their agglomerates. At the same time, the grains, which have become shiny black after irradiation, exhibit an increase of both the real and the imaginary part of . ²⁷Al-NMR spectra of the irradiated powder present a Knight-shifted line at 1600(50) ppm, close to the position of bulk metallic Al, and corresponding to a concentration of c(Al) . In addition, the main hydride line differs from that before irradiation, demonstrating an alteration of environmental symmetry. The irradiation induces also a change in shape and width of the ¹H-NMR line, another indication of symmetry change in the lattice. Finally, a refined X-ray single-crystal structure analysis of the irradiated cuboid indicates a change of structure from trigonal R -3 c to R -3, with a loss of mirror symmetry for the two Al sites caused by the introduction of Al-defects in the vicinity of one of them. Received: 20 October 1997 / Revised: 24 December 1997 / Accepted: 30 January 1998     

A Statistical Model for Describing Spectral Diffusion Effects in Electron Spin Echo (ESE) and Electron Nuclear Double Resonance (ENDOR) Experiments

A statistical model for an EPR line broadened by dipolar electron-nuclear interaction is proposed. This makes it possible for the effect of spectral diffusion on the width and intensity of ENDOR signals to be determined from electron spin echo experiments. In this paper, various ENDOR mechanisms are discussed in addition to a calculation of the variation in both Boltzmann factor and spin temperature due to the spectral diffusion effect.