A novel use of hyperfine structure in the electron paramagnetic resonance of interacting pairs of paramagnetic defects in diamond

It is the hyperfine structure of ¹⁴N and ¹³C in the electron paramagnetic resonance (EPR) spectrum which indicates that the unpaired electron of a single substitutional nitrogen atom in diamond is in one of the four anti-bonding N-C orbitals. We show that, for diamonds containing a very high concentration of nitrogen, the hyperfine structure of interacting pairs of nitrogen atoms indicates that for close neighbours there are unique orientations of the constituent N-C bonds, while at larger distances the orientations are random. This revised version was published online in August 2006 with corrections to the Cover Date.     

An electron paramagnetic resonance study of LDPE irradiated with high-energy electron beam

Cross-linking of the polyethylene was performed with a high-energy electron beam. Electron paramagnetic resonance spectroscopy was used to study the lifetime of unpaired electron in the irradiated samples. Time-dependent electrical parameters are investigated for the cross-linked low-density polyethylene. Both dielectric constant and dielectric strength almost remained unchanged, but for short times, the volume resistivity and loss factor increased and decreased, respectively. It is predicted that for lifetime longer than 48 h, the electrical parameters were constant. It is believed that the variation of some electrical properties during time is due to the effects of trapped electrons.     

Nuclear polarization by electron paramagnetic resonance in paramagnetic crystals

The possibility of the polarization of nuclei in paramagnetic salts by saturation of electron paramagnetic resonance is theoretically analyzed. The proposed method assumes saturation of the forbidden transition of the typeM=±1, m=±1, ±2, for mutually perpendicular external magnetic and high-frequency fields. The analysis is carried out for the case of a large quadrupole moment of the nucleus. The degree of orientation attained is comparable in order of magnitude with Overhauser's method. This method is particularly suitable for the polarization of nuclei of transuranium elements.

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. M=± 1, m==±1, ±2 . . . .

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In conclusion the author would like to thank J. Burget, J. ajko, M. Kolá and M. ott for helping in the laborious solution of system (16).     

Multifrequency electron paramagnetic resonance of ultramarine blue

Electron paramagnetic resonance spectra of the S^3/? radical center in ultramarine blue over a factor of about 2500 in frequency (258 MHz to 670 GHz) reveal a substantially Lorentzian shape, without resolution of g anisotropy. Variable temperature measurements found that the line width is independent of temperature, within experimental uncertainty, up to about 90 K at 9.5 GHz and between ca. 5 K and room temperature at 95 and 217 GHz, as expected for an exchange-narrowed signal. Analysis of the increase in the low-temperature line width as a function of frequency above 9 GHz is consistent with an exchange interaction of about 2· 10^?2 K. The line width increases as frequency is decreased from 2.7 GHz to 258 MHz which is attributed to the contribution from nonsecular terms that has been denoted the “10/3” effect.     

Precisiong-factor measurements of electron paramagnetic resonance standards

An attempt is made to measureg-factors of electrons in EPR standard samples with the lowest obtainable uncertainty. An experimental equipment for preciseg-factor measurements is described, working at microwave frequencies in the 9 and 36 GHz region, and at room temperature. The course of the measuring process is mentioned in some detail and the sources of errors, which arise during the measurement, are discussed. As an example, the determination ofg-factors of certain EPR standards (using DPPH single crystals and powdered charred dextrose) is presented. No dispersion ofg-factor value has been observed between 9 and 36 GHz.     

Lattice dynamic effects in electron paramagnetic resonance

The electron-phonon interaction for a paramagnetic impurity in an insulating crystal is derived and from that an electron-electron interaction in a higher order is considered. An attempt is made to provide a unified presentation of the effect of phonons on the parameters measured in an electron-paramagnetic resonance experiment. The phonon-induced corrections to the zero-field splitting, the hyperfine field, the superhyperfine splitting and line intensities is reviewed theoretically along with experimental data. Both the point charge and covalent models are discussed. The effect of local and resonance modes is calculated and discussed in terms of isotope effect. Some related problems of the energy levels, dispersion, screening and phonon force are also included in appendices.     

Targeted-ROI imaging in electron paramagnetic resonance imaging

Electron paramagnetic resonance imaging (EPRI) is a technique that has been used for in vivo oxygen imaging of small animals. In continuous wave (CW) EPRI, the measurement can be interpreted as a sampled 4D Radon transform of the image function. The conventional filtered-backprojection (FBP) algorithm has been used widely for reconstructing images from full knowledge of the Radon transform acquired in CW EPRI. In practical applications of CW EPRI, one often is interested in information only in a region of interest (ROI) within the imaged subject. It is desirable to accurately reconstruct an ROI image only from partial knowledge of the Radon transform because acquisition of the partial data set can lead to considerable reduction of imaging time. The conventional FBP algorithm cannot, however, reconstruct accurate ROI images from partial knowledge of the Radon transform of even dimension. In this work, we describe two new algorithms, which are referred to as the backprojection filtration (BPF) and minimum-data filtered-backprojection (MDFBP) algorithms, for accurate ROI-image reconstruction from a partial Radon transform (or, truncated Radon transform) in CW EPRI. We have also performed numerical studies in the context of ROI-image reconstruction of a synthetic 2D image with density similar to that found in a small animal EPRI. This demonstrates both the inadequacy of the conventional FBP algorithm and the success of BPF and MDFBP algorithms in ROI reconstruction. The proposed ROI imaging approach promises a means to substantially reduce image acquisition time in CW EPRI.     

Carbon-based standards for electron paramagnetic resonance spectroscopy

In order to meet the need for a good new EPR intensity andg-value standard whose paramagnetic species are carbon-based radicals, several materials were investigated, including coal, fusinite (a coal maceral), and several carbohydrate chars. Of the prototypical standards prepared, a chemically-treated fusinite is recommended as most suitable because of its chemical stability, spin density, EPR signal line shape and line width, microwave power saturation characteristics, availability, and homogeneity. Effects of dilution with KBr, KCl, and polymer are negligible, although the line width is broadened in the presence of paramagnetic gases. Several model standard compounds have been prepared in a polymer matrix to minimize changes in packing density over time.     

An electron paramagnetic resonance study of conformational substate distribution in high spin heme-proteins

The electron paramagnetic resonance spectra of high spin ferric horse myoglobin and human hemoglobin have been analyzed by computer simulation in terms of a distribution of the metal ion crystal field energies Δ₁ and Δ₂. The widths of these distributions have been put into relation 0 to the distribution of the conformational substates which may be sampled by the biomolecules during their physiological activity and become eventually arrested at low temperature. These distributions are found to be dependent upon both the solvent used and the cooling history to which the samples were submitted. The results are discussed in connection with the physical analogies displayed by these biomolecules and the glassy systems in general.     

An X-band time domain electron paramagnetic resonance spectrometer

A computer-controlled X-band time domain electron paramagnetic resonance (EPR) spectrometer, with a time resolution of the order of 0.5μsec, has been constructed with many of the crucial microwave components designed and fabricated by the Microwave Engineering Group of TIFR. The spectrometer operates either in a microwave power pulsed mode for determination of spin-lattice relaxation times by the saturation recovery technique or in the kinetic mode for determination of the time dependence of EPR signal after laser excitation. It has an automatic frequency control, an automatic phase control and, most importantly, a field-frequency lock which ensures good stability of the EPR line positions enabling signal averaging for extended periods. The constructional details of the spectrometer and its performance in both the modes are described here by reporting results on certain typical systems.     

The continuous wave electron paramagnetic resonance experiment revisited

When the modulation frequency used in continuous wave electron paramagnetic resonance (cw EPR) spectroscopy exceeds the linewidth, modulation sidebands appear in the spectrum. It is shown theoretically and experimentally that these sidebands are actually multiple photon transitions, sigma(+)+kxpi, where one microwave (mw) sigma(+) photon is absorbed from the mw radiation field and an arbitrary number k of radio frequency (rf) pi photons are absorbed from or emitted to the modulation rf field. Furthermore, it is demonstrated that both the derivative shape of the lines in standard cw EPR spectra and the distortions due to overmodulation are caused by the unresolved sideband pattern of these lines. The single-photon transition does not even give a contribution to the first-harmonic cw EPR signal. Multiple photon transitions are described semiclassically in a toggling frame and their existence is proven using second quantization. With the toggling frame approach and perturbation theory an effective Hamiltonian for an arbitrary sideband transition is derived. Based on the effective Hamiltonians an expression for the steady-state density operator in the singly rotating frame is derived, completely describing all sidebands in all modulation frequency harmonics of the cw EPR signal. The relative intensities of the sidebands are found to depend in a very sensitive way on the actual rf amplitude and the saturation of single sidebands is shown to depend strongly on the effective field amplitude of the multiple photon transitions. By comparison with the analogous solutions for frequency-modulation EPR it is shown that the field-modulation and the frequency-modulation technique are not equivalent. The experimental data fully verify the theoretical predictions with respect to intensities and lineshapes.     

Nickel in silicon studied by electron paramagnetic resonance

We have investigated nickel in silicon samples with a wide range of initial doping concentrations by EPR, DLTS and photo-EPR techniques. Our results show that the two different Ni-centers which were observed previously by EPR, but whose structure could not be interpreted unambiguously, are both associated with Ni in a substitutional position. They are distinguished by their charges and by slightly different displacements from the ideal substitutional site. A model for the Ni⁺_s-center is suggested which explains the symmetry of this center. PACS 71.55.Cn; 76.30.Fc     

Detection of electron paramagnetic resonance absorption using frequency modulation

A frequency modulation (FM) method was developed to measure electron paramagnetic resonance (EPR) absorption. The first-derivative spectrum of 1,1-diphenyl-2-picrylhydrazyl (DPPH) powder was measured with this FM method. Frequency modulation of up to 1.6 MHz (peak-to-peak) was achieved at a microwave carrier frequency of 1.1 GHz. This corresponds to a magnetic field modulation of 57microT (peak-to-peak) at 40.3 mT. By using a tunable microwave resonator and automatic control systems, we achieved a practical continuous-wave (CW) EPR spectrometer that incorporates the FM method. In the present experiments, the EPR signal intensity was proportional to the magnitude of frequency modulation. The background signal at the modulation frequency (1 kHz) for EPR detection was also proportional to the magnitude of frequency modulation. An automatic matching control (AMC) system reduced the amplitude of noise in microwave detection and improved the baseline stability. Distortion of the spectral lineshape was seen when the spectrometer settings were not appropriate, e.g., with a lack of the open-loop gain in automatic tuning control (ATC). FM is an alternative to field modulation when the side-effect of field modulation is detrimental for EPR detection. The present spectroscopic technique based on the FM scheme is useful for measuring the first derivative with respect to the microwave frequency in investigations of electron-spin-related phenomena.     

Application of electron paramagnetic resonance to the study of Cu2+ ions in Cu-Na ion-exchanged glasses

The copper ion-exchange process in two different silicate glasses is experimentally studied by means of electron paramagnetic resonance analysis. Differences in the environment of divalent copper ions are found depending on the substrate. The Cu²⁺ concentration in-depth profile is determined and compared to the total copper diffusion profile as determined from secondary ion mass spectrometry. Received: 12 February 1998 / Accepted: 5 January 1999 / Published online: 7 April 1999