Electron nuclear quadruple resonance for assignment of overlapping spectra

Multiple resonance methods are important tools in EPR for revealing the network of hyperfine levels of free radicals and paramagnetic centers. The variations of electron nuclear double resonance (ENDOR) or electron spin-echo envelope modulation (ESEEM) techniques help to correlate nuclear frequencies with each other. These methods have limited utility when there is extensive overlap or suspected overlap in the EPR spectrum between different species or different orientations. In the ENDOR spectrum, overlap and second-order shifts of lines also leads to ambiguity in assignment and interpretation. A new electron nuclear multiple resonance method is presented here that is based on population transfer ENDOR. It is a quadruple resonance method that correlates ENDOR lines and reveals the network of hyperfine levels in samples with unoriented paramagnetic species and in samples with overlapping EPR or ENDOR lines.     

Electron paramagnetic resonance detection of the giant concentration of nitrogen vacancy defects in sintered detonation nanodiamonds

A giant concentration of nitrogen vacancy defects has been revealed by the electron paramagnetic resonance (EPR) method in a detonation nanodiamond sintered at high pressure and temperature. A high coherence of the electron spins at room temperature has been observed and the angular dependences of the EPR spectra indicate the complete orientation of the diamond system.     

Determination of T1-spin-lattice relaxation time in a two-level system by continuous wave multiquantum electron paramagnetic resonance spectroscopy in a presence of tetrachromatic microwave irradiation

Applicability of continuous wave multiquantum EPR methods to study relaxation times at X-band is examined. Multiquantum transitions excited in a two-level system by tetrachromatic irradiation are used for these studies. The Bloch equation model is applied to simulate lineshapes of the three quantum transitions as a function of frequency difference between exciting fields. The dependence of multiquantum transition signals on relaxation times and microwave amplitude is shown. On this basis a method of deducing relaxation times from these signals is formulated. The case of a homogeneously and inhomogeneously broadened resonance line is considered. Two experimental methods are used to verify the proposed hypothesis: the X-band continuous wave multiquantum EPR with four frequencies microwave field and saturation recovery EPR. The values of T₁ obtained from CW MQ EPR and SR EPR are compared.     

Generalization of the lineshape useful in magnetic resonance spectroscopy

A new lineshape function is derived from the Tsallis distribution to describe electron paramagnetic resonance (EPR) spectra, and possibly nuclear magnetic resonance (NMR) spectra as well. This lineshape generalizes the Gaussian and Lorentzian lineshapes that are widely used in simulations. The main features of this lineshape function are presented: the normalization, moments, and first derivative. A number of experimental EPR spectra are compared with the results of simulations employing the new lineshape function. The results show that the new lineshape often provides a better approximation of the experimental spectrum. It is also shown that the new parameter of the lineshape function can be used to quantify the intermolecular spin-spin interactions.     

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.     

Spin-labeled photosynthetic reaction centers fromRhodobacter sphaeroides studied by electron paramagnetic resonance spectroscopy and molecular dynamics simulations

A new strategy has been applied that combines molecular dynamics (MD) simulations and electron paramagnetic resonance (EPR) spectroscopy to study the structure and conformational dynamics of the spin-labeled photosynthetic reaction center (RC) ofRhodobacter sphaeroides. This protein serves here as a model system to demonstrate the applicability of this new methodology. The RC contains five native cysteines and EPR experiments show that only one cysteine, located on the H subunit, is accessible for spin labeling. The EPR spectra calculated from MD simulation trajectories of spin labels bound to the native cysteines C156 and C234 in subunit H reveal that only the spin label side chain at position 156 provides a spectrum which agrees with the experimental EPR spectrum.     

Observation of electric quadrupole spin resonance of Ho<Superscript>3+</Superscript> impurity ions in synthetic forsterite

The anomalous dependence of the electron paramagnetic resonance (EPR) line shape on the microwave power in the resonator has been found when studying the continuous-wave EPR spectra of impurity holmium ions in synthetic forsterite on an ELEXSYS E 580 EPR spectrometer. The power-threshold transition from the conventional lines being the derivatives of the spectral line contours to the spectral line contours themselves has been observed as the power increased. The properties of the anomalous EPR lines are qualitatively explained assuming that the resonance electric quadrupole transitions take place between the electron spin levels.     

Electron paramagnetic resonance in neutron-transmutation-doped semiconductors with a changed isotopic composition

Potential applications of electron paramagnetic resonance (EPR) for investigating and controlling the process of neutron transmutation doping (NTD) of semiconducting germanium, silicon, and silicon carbide are discussed. It is shown that EPR enables one to control the process of annealing of radiation-induced defects in semiconductors subject to neutron irradiation and to detect the shallow donors restored in the process of annealing of donor-compensating defects by observing EPR signals from these donors. EPR can be used to separately detect isolated donors and clusters of two, three, and more exchange-bound donor atoms and thereby determine the degree of nonuniformity of the impurity distribution over the crystal. Neutron transmutation doping is demonstrated to produce a fairly uniform arsenic-donor distribution in a germanium crystal. It is argued that semiconductors enriched in the selected isotopes should be used for NTD. The results of an investigation of phosphorus donors in silicon carbide are presented.     

Interaction of electromagnetic waves with nonlinear substance layer under conditions of electron paramagnetic resonance in millimeter waves

Trancated equations have been obtained by the Green's functions method for a slowly varying amplitude of a transverse magnetic field component in a paramagnetic layer under conditions of the electron paramagnetic resonance (EPR). A magnetic susceptibiliti of the substence has been found from the Bloch equation for a homogeneously line breadth of the EPR. In a stationary case a solution of a nonlinear boundary-value problem is redused to a solution of two boundary problems for amplitude and phase equations. It is shown that unstable regimes of the electrodynamic system under inves tigation are possible.Electrodynamic characteristics of a nonlinear resonator of the Fabry-Pero type filled with a saturated paramagnetic medium have been analyzed numerically in a non-stationery case.     

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.     

High-speed data acquisition system and receiver configurations for time-domain radiofrequency electron paramagnetic resonance spectroscopy and imaging

Design strategies, system configuration, and operation of a dual-channel data acquisition system for a radiofrequency (RF) time-domain electron paramagnetic resonance (EPR) spectrometer/imager operating at 300 MHz are described. This system wasconfigured to incorporate high-speed analog-to-digital conversion (ADC) and summation capabilities with both internal and external triggering via GPIB interface. The sampling rate of the ADC is programmable up to a maximum of 1 GS/s when operating in a dual-channel mode or 2 GS/s when the EPR data are collected in a single-channel mode. By using high-speed flash ADCs, a pipelined 8-bit adder, and a 24-bit accumulator, a repetition rate of 230 kHz is realized to sum FIDs of 4096 points. The record length is programmable up to a maximum of 8K points and a large number of FIDs (2(24)) can be summed without overflow before the data can be transferred to a host computer via GPIB interface for further processing. The data acquisition system can operate in a two-channel (quadrature) receiver mode for the conventional mixing to baseband. For detection using the single-channel mode, the resonance signals around the center frequency of 300 MHz were mixed with a synchronized local oscillator of appropriate frequency leading to an intermediate frequency (IF) which is sampled at a rate of 2 GS/s. Comparison of quadrature-mode and an IF-mode operation for EPR detection is presented by studying the FID signal intensity across a bandwidth of 10 MHz and as a function of transmit RF power. Imaging of large-sized phantoms accommodated in appropriately sized resonators indicates that IF-mode operation can be used to obtain distortion-free images in resonators of size 50 mm diameter and 50 mm length.     

Integration of digital signal processing technologies with pulsed electron paramagnetic resonance imaging

The integration of modern data acquisition and digital signal processing (DSP) technologies with Fourier transform electron paramagnetic resonance (FT-EPR) imaging at radiofrequencies (RF) is described. The FT-EPR system operates at a Larmor frequency (L(f)) of 300MHz to facilitate in vivo studies. This relatively low frequency L(f), in conjunction with our approximately 10MHz signal bandwidth, enables the use of direct free induction decay time-locked subsampling (TLSS). This particular technique provides advantages by eliminating the traditional analog intermediate frequency downconversion stage along with the corresponding noise sources. TLSS also results in manageable sample rates that facilitate the design of DSP-based data acquisition and image processing platforms. More specifically, we utilize a high-speed field programmable gate array (FPGA) and a DSP processor to perform advanced real-time signal and image processing. The migration to a DSP-based configuration offers the benefits of improved EPR system performance, as well as increased adaptability to various EPR system configurations (i.e., software configurable systems instead of hardware reconfigurations). The required modifications to the FT-EPR system design are described, with focus on the addition of DSP technologies including the application-specific hardware, software, and firmware developed for the FPGA and DSP processor. The first results of using real-time DSP technologies in conjunction with direct detection bandpass sampling to implement EPR imaging at RF frequencies are presented.     

Electron paramagnetic resonance of hydrogen in silicon

A review of the investigations by means of electron paramagnetic resonance (EPR) of hydrogen and hydrogen-related defects in crystalline silicon is presented. The main features of the EPR center Si-AA9 (bond-centered hydrogen), which is known as the hydrogenic analogue of the anomalous muonium (Mu^*) in silicon, are discussed. It was found that the process of annealing the AA9 center is characterized by an activation energy, E = 0.48 ± 0.04 eV with a second-order pre-exponential factor, K₀ = (1.25 ± 2.5) × 10^-7 cm³/s.

A detailed investigation by EPR of the defect (Si-AA1), which we identify as the hydrogen-related shallow donor in a positive charge state, is also presented. In particular it is shown that the H-related shallow donor is a helium-like center and its wave function has C_2v symmetry. Moreover, the main features of the series of EPR spectra in silicon characteristic for the implantation of hydrogen are presented.     

Potential of electron paramagnetic resonance to study Einstein-Podolsky-Rosen-Bohm pairs

The potential of electron paramagnetic resonance (EPR) methods to study the correlation of the states of two noninteracting spins prepared in the singlet state (Einstein-Podolsky-Rosen-Bohm [EPRB] pairs) is discussed. EPR methods with a selective excitation of spins in the EPRB pairs allow one, in principle, to reveal this correlation of spin states if single-spin measurements are performed. However, it is illustrated that the conventional ensemble EPR experiments, when the average values of projections of the spin moments are observables, fail in studying the correlation of spins in EPRB pairs. An exploitation of the EPR phenomenon to study the correlation of spins for ensembles of EPRB pairs needs some modifications of the experimental approach: either the indirect detection of EPR signals (new observables) should be used or the EPRB pairs should be transferred to another state when the spin-spin interaction becomes essential, while EPR observables manifest the spin correlation in the precursor EPRB pair state. In this respect it appears that in spin chemistry many results were already obtained which demonstrate that it is a reality that two spins might occupy the “entangled” (correlated) state, when there is no interaction between them. The results obtained in spin chemistry confirm the quantum mechanical predictions for spin-correlated pairs of spins which can be considered as a realization of EPRB pairs.     

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.     

Luminescence and magnetic resonance in post-hydrogenated microcrystalline silicon

We report photoluminescence, EPR and ODMR studies of plasma hydrogenated LPCVD microcrystalline silicon thin films. Apart from the dangling bond EPR resonance which is similar to that observed in a-Si : H, and possibly the emission at 1.3 eV, we find emission bands and resonance signals quite unlike those observed in normal c-Si and a-Si : H. We conclude that μc-Si : H cannot be regarded purely as crystallites of pure silicon embedded in a matrix of a-Si : H.     

Features of EPR Application to Systems Containing Paramagnetic Centers and Ferromagnetic Nanoparticles

The scope of the electron paramagnetic resonance (EPR) technique in catalysis is often limited because of the presence of the ferromagnetic nanoparticles in many catalytic systems. The present work gives an effective method to discriminate solid-state EPR spectra in the microwave resonance absorption while investigating such systems. The approach is based on the different features of the EPR spectra and ferromagnetic resonance absorption that are simultaneously observed in the system.     

Non-Markovian theory of electron paramagnetic resonance in localized and quasi-localized electron spins via an example of manganites with colossal magnetoresistance

An approach based on the memory functions formalism is applied to derive non-Markovian equations of motion for the magnetization components of localized and quasi-localized electron spins under electron paramagnetic resonance (EPR) conditions using the example of manganites with colossal magnetoresistance. General Hasegawa-Bloch-type equations are applied to describe certain experimental data concerning the shape and the width of EPR lines and the longitudinal and transverse relaxation rates. Particular cases of these equations reproduce well-known theoretical results concerning EPR in manganites with colossal magnetoresistance. The results obtained explain certain well-known experimental phenomena and may stimulate further research.     

Electron paramagnetic resonance radiation dosimetry in fingernails

There is now an increased need for accident dosimetry due to the increased risk of significant exposure to ionizing radiation from terrorism or accidents. In such scenarios, dose measurements should be made in individuals rapidly and with sufficient accuracy to enable effective triage. Electron paramagnetic resonance (EPR) is a physical method of high potential for meeting this need, providing direct measurements of the radiation-induced radicals, which are unambiguous signatures of exposure to ionizing radiation. For individual retrospective dosimetry, EPR in tooth enamel is a proven and effective technique when isolated teeth can be obtained. There are some promising developments that may make these measurements feasible without the need to remove the teeth, but their field applicability remains to be demonstrated. However, currently it is difficult under emergency conditions to obtain tooth enamel in sufficient amounts for accurate dose measurements. Since fingernails are much easier to sample, they can be used in potentially exposed populations to determine if they were exposed to life-threatening radiation doses. Unfortunately, only a few studies have been carried out on EPR radiation-induced signals in fingernails, and, while there are some promising aspects, the reported results were generally inconclusive. In this present paper, we report the results of a systematic investigation of the potential use of fingernails as retrospective radiation dosimeters.