Direct-detected rapid-scan EPR at 250 MHz

EPR spectra at 250 MHz for a single crystal of lithium phthalocyanine (LiPc) in the absence of oxygen and for a deoxygenated aqueous solution of a Nycomed triarylmethyl (trityl-CD3) radical were obtained at scan rates between 1.3 x 10(3) and 3.4 x 10(5)G/s. These scan rates are rapid relative to the reciprocals of the electron spin relaxation times (LiPc: T1 = 3.5 micros and T2 = 2.5 micros; trityl: T1 = 12 micros and T2 = 11.5 micros) and cause characteristic oscillations in the direct-detected absorption spectra. For a given scan rate, shorter values of T2 and increased inhomogeneous broadening cause less deep oscillations that damp out more quickly than for longer T2. There is excellent agreement between experimental and calculated lineshapes and signal amplitudes as a function of radiofrequency magnetic field (B1) and scan rate. When B1 is adjusted for maximum signal amplitude as a function of scan rate, signal intensity for constant number of scans is enhanced by up to a factor of three relative to slow scans. The number of scans that can be averaged in a defined period of time is proportional to the scan rate, which further enhances signal amplitude per unit time. Longer relaxation times cause the maximum signal intensity to occur at slower scan rates. These experiments provide the first systematic characterization of direct-detected rapid-scan EPR signals.     

Deconvolution of sinusoidal rapid EPR scans

In rapid scan EPR the magnetic field is scanned through the signal in a time that is short relative to electron spin relaxation times. Previously it was shown that the slow-scan lineshape could be recovered from triangular rapid scans by Fourier deconvolution. In this paper a general Fourier deconvolution method is described and demonstrated to recover the slow-scan lineshape from sinusoidal rapid scans. Since an analytical expression for the Fourier transform of the driving function for a sinusoidal scan was not readily apparent, a numerical method was developed to do the deconvolution. The slow scan EPR lineshapes recovered from rapid triangular and sinusoidal scans are in excellent agreement for lithium phthalocyanine, a trityl radical, and the nitroxyl radical, tempone. The availability of a method to deconvolute sinusoidal rapid scans makes it possible to scan faster than is feasible for triangular scans because of hardware limitations on triangular scans.     

Application of the Raman heterodyne technique for the detection of EPR and ENDOR

Raman heterodyne detection is a coherent optical-RF double resonance technique where the optical and RF fields induce coherence within a three level system and a resultant Raman field is measured using heterodyne detection. This approach has been used previously to detect NMR and more recently EPR. In this paper the parameters that affect the amplitude and signal to noise ratio of the Raman heterodyne signals are considered. The power levels in relation to the oscillator strength and dephasing times, the amplitude and spectrum of the laser frequency jitter in relation to the optical homogeneous linewidths and holeburning rates, and the sample properties such as absorption strength and optical quality, are all factors that affect the Raman signal. The presentation is focused on the Raman heterodyne detected EPR of the nitrogen-vacancy pair centre in diamond making comparisons with Raman heterodyne detected NMR signals obtained for rare earth ion systems. RF-RF double resonance studies, RF holeburning and ENDOR, which give information about the hyperfine levels are also reported for the nitrogen-vacancy centre. The resonance frequencies are in agreement with those predicted from the spin Hamiltonian. The factors affecting the lineshapes and relative intensities of the double resonance signals are discussed.     

Impact of resonator on direct-detected rapid-scan EPR at 9.8 GHz

Rapid-scan electron paramagnetic resonance spectra at 9.8 GHz were obtained on a Bruker E580 spectrometer. Spectra of lithium phthalocyanine (LiPc) needles (T ₁=8 μs,T ₂=3.4 μs) and of a 0.2 mM aqueous solution of Nycomed triarylmethyl (trityl-CD₃) radical (T ₁=11.5 μs,T ₂=8 μs) were recorded at scan rates between 3.4·10³ and 7.5·10⁵ G/s at the center of sinusoidal scans. Signals for LiPc were obtained with a split-ring resonator, a rectangular resonator and a dielectric resonator. At faster scan rates the small bandwidth of the high-Q dielectric resonator filters, out high-frequency components of the rapid-scan signals. Field inhomogeneities induced by the rapidly changing magnetic field increase with scan rate and are greater with the dielectric and split-ring resonantors than with the rectangular resonator. Data for trityl-CD₃ were recorded with the rectangular resonator. The extended trityl sample, about 3 mm long, shows larger effects of magnetic field inhomogeneities than the small LiPc crystals.     

X-band rapid-scan EPR of nitroxyl radicals

X-band rapid-scan EPR spectra were obtained for dilute aqueous solutions of nitroxyl radicals (15)N-mHCTPO (4-hydro-3-carbamoyl-2,2,5,5-tetra-perdeuteromethyl-pyrrolin-1-(15)N-oxyl-d(12)) and (15)N-PDT (4-oxo-2,2,6,6-tetra-perdeuteromethyl-piperidinyl-(15)N-oxyl-d(16)). Simulations of spectra for (15)N-mHCTPO and (15)N-PDT agreed well with the experimental spectra. As the scan rate is increased in the rapid scan regime, the region in which signal amplitude increases linearly with B(1) extends to higher power and the maximum signal amplitude increases. In the rapid scan regime, the signal-to-noise for rapid-scan spectra was about a factor of 2 higher than for unbroadened CW EPR, even when the rapid scan spectra were obtained in a mode that had only 4% duty cycle for data acquisition. Further improvement in signal-to-noise per unit time is expected for higher duty cycles. Rapid scan spectra have higher bandwidth than CW spectra and therefore require higher detection bandwidths at faster scan rates. However, when the scan rate is increased by increasing the scan frequency, the increase in noise from the detection bandwidth is compensated by the decrease in noise due to increased number of averages per unit time. Because of the higher signal bandwidth, lower resonator Q is needed for rapid scan than for CW, so the rapid scan method is advantageous for lossy samples that inherently lower resonator Q.     

Comparison of Continuous Wave, Spin Echo, and Rapid Scan EPR of Irradiated Fused Quartz

The E' defect in irradiated fused quartz has spin lattice relaxation times (T(1)) about 100 to 300 μs and spin-spin relaxation times (T(2)) up to about 200 μs, depending on the concentration of defects and other species in the sample. These long relaxation times make it difficult to record an unsaturated continuous wave (CW) electron paramagnetic resonance (EPR) signal that is free of passage effects. Signals measured at X-band (~9.5 GHz) by three EPR methods: conventional slow-scan field modulated EPR, rapid scan EPR, and pulsed EPR, were compared. To acquire spectra with comparable signal-to-noise, both pulsed and rapid scan EPR require less time than conventional CW EPR. Rapid scan spectroscopy does not require the high power amplifiers that are needed for pulsed EPR. The pulsed spectra, and rapid scan spectra obtained by deconvolution of the experimental data, are free of passage effects.     

A new strategy for fast radiofrequency CW EPR imaging: direct detection with rapid scan and rotating gradients

Rapid field scan on the order of T/s using high frequency sinusoidal or triangular sweep fields superimposed on the main Zeeman field, was used for direct detection of signals without low-frequency field modulation. Simultaneous application of space-encoding rotating field gradients have been employed to perform fast CW EPR imaging using direct detection that could, in principle, approach the speed of pulsed FT EPR imaging. The method takes advantage of the well-known rapid-scan strategy in CW NMR and EPR that allows arbitrarily fast field sweep and the simultaneous application of spinning gradients that allows fast spatial encoding. This leads to fast functional EPR imaging and, depending on the spin concentration, spectrometer sensitivity and detection band width, can provide improved temporal resolution that is important to interrogate dynamics of spin perfusion, pharmacokinetics, spectral spatial imaging, dynamic oxymetry, etc.     

Second-harmonic detection with tunable diode lasers — Comparison of experiment and theory

A series of experiments are carried out by current modulating a tunable diode laser, and slowly ramping the wavelength to scan weak absorption lines in gases at pressures ranging from 2 to 60 Torr. A lock-in amplifier detects the second harmonic (2f) of the modulation frequency, and the experimental 2f signals are compared with theory. Detailed measurements are made on Lorentzian, Voigt, and Gaussian line profiles, over a wide range of modulation amplitudes. Excellent agreement between experiment and calculation is obtained in all cases. This quantitative understanding enables one to derive true lineshapes and linewidths of very weak absorption lines from measurements of 2f lineshapes only. Results are applicable to trace gas detection using tunable diode lasers, and to other areas of spectroscopy and magnetic resonance where harmonic detection techniques are routinely employed to monitor weak signals.This work was supported in part by the National Science and Engineering Research Council, Canada     

Frequency-multiplexed gas sensing using chirped laser molecular spectroscopy

A method for frequency-multiplexed multi-sample gas sensing is presented. It enables measuring multiple samples placed simultaneously in the setup, without any optical or mechanical switching. Samples are measured using heterodyne detection and signal from each sensing path is encoded at different carrier frequency. Subsequently, a signal from particular sample is retrieved through heterodyne beatnote demodulation at unique frequency. This technique is particularly suitable for real-time calibration of the sensor through a sequential (or simultaneous) detection of three signals: from unknown sample, reference sample and baseline. Basic setup is demonstrated and proof-of-concept experiments are presented. Very good agreement with spectra measured using standard tunable diode absorption spectroscopy is obtained.     

Background removal procedure for rapid scan EPR

In rapid scan EPR the changing magnetic field creates a background signal with components at the scan frequency and its harmonics. The amplitude of the background signal increases with scan width and is more significant for weak EPR signals such as are obtained in the presence of magnetic field gradients. A procedure for distinguishing this background from the EPR signal is proposed, mathematically described, and tested for various experimental conditions.     

Rapid frequency scan EPR

In rapid frequency scan EPR with triangular scans, sufficient time must be allowed to insure that the magnetization in the x, y plane decays to baseline at the end of the scan, which typically is about 5T(2) after the spins are excited. To permit relaxation of signals excited toward the extremes of the scan the total scan time required may be much longer than 5T(2). However, with periodic, saw-tooth excitation, the slow-scan EPR spectrum can be recovered by Fourier deconvolution of data recorded with a total scan period of 5T(2), even if some spins are excited later in the scan. This scan time is similar to polyphase excitation methods. The peak power required for either polyphase excitation or rapid frequency scans is substantially smaller than for pulsed EPR. The use of an arbitrary waveform generator (AWG) and cross loop resonator facilitated implementation of the rapid frequency scan experiments reported here. The use of constant continuous low B(1), periodic excitation waveform, and constant external magnetic field is similar to polyphase excitation, but could be implemented without the AWG that is required for polyphase excitation.     

Nonequivalent spectra of unpaired electrons in field and frequency modulation

We report a difference in the spectral lineshapes of continuous-wave (CW) electron paramagnetic resonance (EPR) spectroscopy between field and frequency modulation. This finding addresses the long-standing question of the effect of modulation in EPR absorption. We compared the first-derivative EPR spectra at 1.1 GHz for lithium phthalocyanine crystals, which have a single narrow linewidth in the EPR absorption spectrum, using field and frequency modulation. The experimental findings suggest that unpaired electrons have different behaviors under perturbation due to field and frequency modulation.     

Physical and Instrumental Considerations in the Use of Lithium Phthalocyanine for Measurements of the Concentration of the Oxygen

The use of crystals of lithium phthalocyanine (LiPc) to measure the concentration of oxygen in vivo and in vitro by electron paramagnetic resonance leads to experimental constraints due to the very narrow EPR lines that may occur (as narrow as 11-13 mG in the absence of O₂), distortions induced by the automatic frequency control system, anisotropy in the spectra (orientation-dependent linewidth is 11-17 mG in the absence of O₂), microwave power saturation, and the effect of physiological motion. These constraints can be overcome if recognized. This article highlights the experimental and theoretical basis of these properties of the EPR signal of LiPc and suggests some technical solutions. It is most important to recognize that paramagnetic species such as LiPc present problems that are not commonly encountered in EPR spectroscopy.     

Detection of undistorted continuous wave (CW) electron paramagnetic resonance (EPR) spectra with non-adiabatic rapid sweep (NARS) of the magnetic field

A continuous wave (CW) electron paramagnetic resonance (EPR) spectrum is typically displayed as the first harmonic response to the application of 100 kHz magnetic field modulation, which is used to enhance sensitivity by reducing the level of 1/f noise. However, magnetic field modulation of any amplitude causes spectral broadening and sacrifices EPR spectral intensity by at least a factor of two. In the work presented here, a CW rapid-scan spectroscopic technique that avoids these compromises and also provides a means of avoiding 1/f noise is developed. This technique, termed non-adiabatic rapid sweep (NARS) EPR, consists of repetitively sweeping the polarizing magnetic field in a linear manner over a spectral fragment with a small coil at a repetition rate that is sufficiently high that receiver noise, microwave phase noise, and environmental microphonics, each of which has 1/f characteristics, are overcome. Nevertheless, the rate of sweep is sufficiently slow that adiabatic responses are avoided and the spin system is always close to thermal equilibrium. The repetitively acquired spectra from the spectral fragment are averaged. Under these conditions, undistorted pure absorption spectra are obtained without broadening or loss of signal intensity. A digital filter such as a moving average is applied to remove high frequency noise, which is approximately equivalent in bandwidth to use of an integrating time constant in conventional field modulation with lock-in detection. Nitroxide spectra at L- and X-band are presented.     

Comparison of maximum entropy and filtered back-projection methods to reconstruct rapid-scan EPR images

Reconstruction of two-dimensional images by filtered back-projection (FBP) and by the maximum entropy method (MEM) was compared for spectral-spatial EPR images with differing signal-to-noise ratios. Experimental projections were recorded using direct-detected rapid scans in the presence of a series of magnetic field gradients. The slow-scan absorption lineshapes were calculated by Fourier deconvolution. A Hamming filter was used in conjunction with FBP, but not for MEM. Imperfections in real experimental data, as well as random noise, contribute to discrepancies between the reconstructed image and experimental projections, which may make it impossible to achieve the customary MEM criterion for convergence. The Cambridge MEM algorithm, with allowance for imperfections in experimental data, produced images with more linear intensity scales and more accurate linewidths for weak signals than was obtained with another MEM method. The more effective elimination of noise in baseline regions by MEM made it possible to detect weak trityl (13)C trityl hyperfine lines that could not be distinguished from noise in images reconstructed by FBP. Another advantage of MEM is that projections do not need to be equally spaced. FBP has the advantages that computational time is less, the amplitude scale is linear, and there is less noise superimposed on peaks in images. It is useful to reconstruct images by both methods and compare results. Our observations indicate that FBP works well when the number of projections is large enough that the star effect is negligible. When there is a smaller number of projections, projections are unequally spaced, and/or signal-to-noise is lower MEM is advantageous.     

Impact of High-Dielectric-Loss Materials on the Microwave Field in EPR Experiments

A dielectric material distorts the microwave field inside an EPR resonator, which results in distortion of the EPR signal from spins inside the material. In this paper, the effects of a spherical bulb filled with a dielectric liquid such as water or a water–ethanol mixture were examined. EPR spectra were recorded for small samples inside and outside of the sphere. The studies include CW and ESE experiments at two microwave frequencies, X band (9.2 GHz) and L band (1.03 GHz). The double integral (area) of an EPR signal depends on[formula]at the position of the sample, causing a large difference in EPR signal intensities between samples in regions of different dielectrics. The phase of the EPR signal also is affected by the presence of the dielectric. These results were compared with three methods of calculating electromagnetic fields (quasi-static method, plane-wave-superposition method, and numerical analysis). Good agreement was found between experimental and calculated results.     

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.     

Electron paramagnetic resonance,electrical resistivity,and magnetization studies in the high Tc superconductors EuBa2Cu3O9−xandEuBa2 (Cu1−yMy)3O9−x (M = Cr,Mn, Fe,Co, Ni,ORZn)

We have measured electron paramagnetic resonance (EPR), electrical resistivity, and dc magnetic susceptibility from 2 K – 300 K for the high T_c oxide superconductor EuBa₂Cu₃O_9−x, either undoped or doped with 3d ions (Cr, Mn, Fe, Ni, Co, or Zn), which presumably substitute at the Cu sites. We have observed an EPR line at low temperatures (T ≤ 40 K), which exhibits an increase in intensity and decrease in field for resonance as the temperature is lowered. The EPR linewidth is also temperature dependent and exhibits a minimum at about 15 K. In some of the samples another EPR signal is observed over the entire temperature range studied, with properties that depend on sample preparation conditions. This signal is likely to be due to small amounts of an additional phase. The behavior and origin of these EPR signals are discussed. The variation of T_c with 3d ion concentration over the range (1 – 8%) is also presented.     

Analysis of the tuning and operation of reflection resonator EPR spectrometers

This paper investigates basic characteristics of the electron paramagnetic resonance (EPR) signal obtained from spectrometers employing reflection resonators. General equations are presented which reveal the phase and amplitude dependence on instrumental parameters of both components of the continuous wave (CW) EPR signal (absorption and dispersion). New phase vector diagrams derived from these general equations are presented for the analysis of the EPR response. The dependence of the phase and absolute value of the CW EPR signal on the local oscillator (LO) phase and on resonator offset and coupling is presented and analyzed. The EPR spectrometer tuning procedures for both balanced and unbalanced heterodyne receivers are analyzed in detail using the new phase diagrams. Extraneous signals at the RF input of the microwave receiver (resulting from circulator leakage and reflections in the resonator transmission line) have been taken into account and analyzed. It is shown that a final tuning condition that corresponds to an extremum of the receiver output as a function of the resonator frequency is necessary and sufficient for the acquisition of pure absorption signal. This condition is universal: it applies to all spectrometer configurations in all frequency ranges. High Frequency EPR spectrometer (130 GHz) data are used to generate experimental phase diagrams that illustrate the theoretical concepts presented in the paper. Conditions are presented under which the absorption signal can be measured with complete suppression of the dispersion, independent of the mutual frequency offset between the microwave source and the EPR sample resonator. Equations describing the approximate relationship between changes of the resonator properties (Q-factor and frequency) and paramagnetic susceptibility are derived and analyzed.     

On Room-Temperature Inversion of EPR Signals of P1 Centre in Synthetic Diamond

Room-temperature inversion of EPR absorption signals of P1 centre in synthetic diamond is studied by the transient nutation technique. Use of the bichromatic field, consisting of a transverse microwave field and longitudinal radio frequency field, allows to investigate the dynamics of P1 centres in the same field configuration as in cw EPR spectrometers. It is shown that the annealing decreases the P1 centre concentration and, respectively, increases the spin-spin relaxation time. As a result, the periodic inversion （nutation） of the P1 centre absorption signal is observed longer. It is assumed that the P1 centre signal inversion, which was previously observed by cw EPR, might be caused by the Bloch-Siegert effect in the bichromatic field.