Amplitude modulated transversal and longitudinal EPR spectroscopy

The amplitude modulated EPR spectroscopy is analyzed both in the time and the frequency domain. The results of numerical calculations and analytical approximate treatments indicate that the signal lineshape is differently affected by relaxation mechanisms when transversal or longitudinal detection is used in spectroscopies with variable frequencies of modulation. Measurements of longitudinally detected electron-spin double resonance obtained in dependence on the frequency of modulation confirm the lineshape expected by the theoretical analysis.     

Kinetic measurements using EPR imaging with a modulated field gradient

EPR imaging with modulated field gradient was applied for the investigation of fast diffusion processes. Three different imaging methods are possible: spectral-temporal, spatio-temporal, and spectral-spatial imaging. The time resolution is on the order of seconds and the spatial resolution is in the micrometer region. The efficiency of this imaging technique is demonstrated for the penetration of the spin probe Tempol in the skin of hairless mice biopsies. The skin is normally protected against the penetration of water soluble substances by the horny layer, a resistive thin lipophilic layer. Overcoming this horny layer for water soluble ingredients is one of the main practical problems for the topical application of pharmaceutics which could be investigated by EPR imaging. Different images represent the penetration behavior of the water soluble Tempol in the skin after treatment with the penetration enhancer DMSO (Dimethylsulfoxide) and after removing the horny layer.     

Absorption measurements using CW MIR NH3 laser

The intensity and half-widths of the v₂ [sP(7,0)] line of ammonia have been measured using an optically pumped CW NH₃ laser. The influence of buffer gas is reported.     

Optimization of magnetic field sweep and field modulation amplitude for continuous-wave EPR oximetry

For continuous-wave electron paramagnetic resonance spectroscopy, what settings of magnetic field sweep width and field modulation amplitude yield the best accuracy in estimated linewidth? Statistical bounds on estimation error presented in this work provide practical guidance: set the sweep width and modulation amplitude to 8 and 4 times the half-width half-maximum linewidth, Γ, respectively. For unknown linewidths in the range [Γ(min),Γ(max)] the worst-case estimation error is minimized by using settings designed for Γ(max). The analysis assumes a Lorentzian lineshape and a constant modulation amplitude across the extent of the irradiated paramagnetic probe. The analytical guidelines are validated using L-band spectroscopy with a particulate LiNc-BuO probe.     

Microwave frequency modulation in CW EPR at W-band using a loop-gap resonator

Loop-gap resonator (LGR) technology has been extended to W-band (94GHz). One output of a multiarm Q-band (35GHz) EPR bridge was translated to W-band for sample irradiation by mixing with 59 GHz; similarly, the EPR signal was translated back to Q-band for detection. A cavity resonant in the cylindrical TE011 mode suitable for use with 100 kHz field modulation has also been developed. Results using microwave frequency modulation (FM) at 50 kHz as an alternative to magnetic field modulation are described. FM was accomplished by modulating a varactor coupled to the 59 GHz oscillator. A spin-label study of sensitivity was performed under conditions of overmodulation and gamma2H1(2)T1T2<1. EPR spectra were obtained, both absorption and dispersion, by lock-in detection at the fundamental modulation frequency (50 kHz), and also at the second and third harmonics (100 and 150 kHz). Source noise was deleterious in first harmonic spectra, but was very low in second and third harmonic spectra. First harmonic microwave FM was transferred to microwave modulation at second and third harmonics by the spins, thus satisfying the "transfer of modulation" principle. The loaded Q-value of the LGR with sample was 90 (i.e., a bandwidth between 3 dB points of about 1 GHz), the resonator efficiency parameter was calculated to be 9.3 G at one W incident power, and the frequency deviation was 11.3 MHz p-p, which is equivalent to a field modulation amplitude of 4 G. W-band EPR using an LGR is a favorable configuration for microwave FM experiments.     

Advantages of digital phase-sensitive detection for upgrading an obsolete CW EPR spectrometer

The replacement of the commonly used analog phase-sensitive detection (PSD) by digital PSD for demodulation of electron paramagnetic resonance (EPR) signals is suggested for upgrading of an out-of-date EPR spectrometer. Connection of the microwave bridge output to a fast analog-digital converter (ADC) eliminates some of the spectrometer’s components: the electronics responsible for analog PSD, ADC for sampling of demodulated signals, and a computer, as well as the usage of some of the spectrometer’s settings. The spectrometer is reduced to a magnet, microwave bridge, and personal computer containing an ADC board. EPR signals digitized for a set of magnetic field positions form a two-dimensional array which is stored in a personal computer. Demodulation and filtering are done numerically to produce a conventional EPR spectrum. In comparison with analog PSD, this numerical approach does not eliminate the out-of-phase component of the signal and the signals at the higher harmonics of the modulation frequency. The details of modernizing the Bruker ER200E SRC EPR spectrometer are discussed to demonstrate these and other advantages of digital demodulation.     

Holographic interferometry using a reference wave with a sinusoidally modulated amplitude

A method of holographic interferometry which uses an amplitude-modulated reference wave is proposed for investigating vibration phases. Sinusoidal amplitude modulation of a reference wave yields hologram fringes which are characterized by a function J²₁(α)cos²Δ, where α and Δ are related to vibration amplitudes and phases on object points, respectively. The resultant fringes indicate that vibration amplitude information and phase information are stored separately. The phase information of the vibration is easily obtained as brightness variations of the fringes, independently of the amplitude information.     

Recent developments in high frequency/high magnetic field CW EPR. Applications in chemistry and biology

A recent review of developments in high magnetic field/high frequency continuous wave electron paramagnetic resonance (EPR) spectroscopy is presented. The main motivations to develop instrumentation beyond “conventional” spectrometers are the desire to increase the spectral resolution and the need for high frequencies in the case of large zero field splitting systems. The potential of high frequency EPR is illustrated with the study of a Mn based spin cluster, which also confirms the need for multifrequency measurements. Examples of high field/high frequency EPR applications to chemistry and biology demonstrate that additional structural information can be obtained with the resolution achieved at 245 GHz.     

Different field distributions obtained with an axicon and an amplitude mask

A combination of an axicon and an amplitude mask is used to obtain an intensity distribution that differs from the typical Bessel one. Experimental and numerical characterization of the field is made for different propagation distances and types of amplitude masks.     

Experimental and theoretical analysis of spurious EPR line features caused by field inhomogeneity

Theory is developed for the detailed lineshapes arising in EPR instruments having inhomogeneous static field. Validity of the theory is established by a comparison with experiment. Results are presented for TE₀₁₁ cavities parallel and transverse to the magnetic field and for the TE₁₀₂ cavity. The results may be generalized with respect to sample size and amount of magnetic field inhomogeneity.     

Absorption spectra of unequal width bilayer graphene nanoribbons in a spatially modulated electric field

The optical absorption spectra of unequal width bilayer graphene nanoribbons can be effectively tuned by a spatially modulated electric field. The absorption spectra exhibit many prominent peaks’ structure owing to the one-dimensional subbands. The number, spectral intensity, and frequency of the absorption peaks depend sensitively on the magnitude, period and phase of the modulated electric potential. The relative displacement between the top and bottom nanoribbons also has strong influence on the spectra. For unequal width bilayer graphene nanoribbons without the interlayer hoppings, there exists an optical selection rule originating from the spatial symmetry of the electron wave functions. Most importantly, such a selection rule can be disrupted by the presence of the interlayer atomic interactions or a spatially modulated electric field. These theoretical predictions can be validated by absorption spectroscopy experiments.     

Model of line preserving field line motions using Euler potentials

We consider behavior of finite magnetic field lines during reconnection processes. We portray field line motions using Euler potentials representation. Here, we propose a new insight into plasma flow fields related with magnetic reconnection. In this approach reconnection is treated as a breakage of magnetic topology, which results in deviation from the line preserving flow regime. We derive constraints and the general equations for these flows. In our approach the flux preserving flows are treated as a special case of line preserving regime. We also derive a constraint on a non-ideal term in Ohm’s Law within diffusion regions, which relates plasma flow with resistivity, and which must hold for non-reconnective diffusion. We also propose a new method of detecting magnetic reconnection.     

Fast 3D spatial EPR imaging using spiral magnetic field gradient

Electron paramagnetic resonance imaging (EPRI) provides direct detection and mapping of free radicals. The continuous wave (CW) EPRI technique, in particular, has been widely used in a variety of applications in the fields of biology and medicine due to its high sensitivity and applicability to a wide range of free radicals and paramagnetic species. However, the technique requires long image acquisition periods, and this limits its use for many in vivo applications where relatively rapid changes occur in the magnitude and distribution of spins. Therefore, there has been a great need to develop fast EPRI techniques. We report the development of a fast 3D CW EPRI technique using spiral magnetic field gradient. By spiraling the magnetic field gradient and stepping the main magnetic field, this approach acquires a 3D image in one sweep of the main magnetic field, enabling significant reduction of the imaging time. A direct one-stage 3D image reconstruction algorithm, modified for reconstruction of the EPR images from the projections acquired with the spiral magnetic field gradient, was used. We demonstrated using a home-built L-band EPR system that the spiral magnetic field gradient technique enabled a 4-7-fold accelerated acquisition of projections. This technique has great potential for in vivo studies of free radicals and their metabolism.     

Self distortion of an amplitude modulated electromagnetic beam in a plasma: Relaxation effects

Following a phenomenological approach an expression for the nonlinear current density in a plasma in the presence of an amplitude-modulated two-dimensional Gaussian (in space) electromagnetic beam has been derived. This expression has been used to study the nonstationary self focusing and resulting self distortion of the beam. The amplitude maxima/minima of the beam are focused by different amounts giving rise to a moving periodic focus and an overmodulation of the beam. The effect of finite values of relaxation times, involved in the nonlinearity, is to shift the amplitude envelope on the time scale. Work partially supported by NSF (USA) and CSIR (India).     

Fast EPR imaging at 300 MHz using spinning magnetic field gradients

Electron paramagnetic resonance imaging (EPRI) technology has rapidly progressed in the last decade enabling many important applications in the fields of biology and medicine. At frequencies of 300-1200 MHz a range of in vivo applications have been performed. However, the requisite imaging time duration to acquire a given number of projections, limits the use of this technique in many in vivo applications where relatively rapid kinetics occur. Therefore, there has been a great need to develop approaches to accelerate EPRI data acquisition. We report the development of a fast low-frequency EPRI technique using spinning magnetic field gradients (SMFG). Utilizing a 300 MHz CW (continuous wave) EPRI system, SMFG enabled over 10-fold accelerated acquisition of image projections. 2D images with over 200 projections could be acquired in less than 3s and with 20s acquisitions good image quality was obtained on large aqueous free radical samples. This technique should be particularly useful for in vivo studies of free radicals and their metabolism.     

An efficient method for measuring atomic and molecular lifetimes using a modulated or deflected CW dye laser beam

By pulse modulating or deflecting a CW dye laser beam, cascade-free lifetime determinations at high spectral resolution can be performed with the decayed-coincidence technique using measuring times of about 1 minute. The method is illustrated by lifetime measurements for the $\text{7}{}^2\text{P}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext><mtext>1</mtext><mtext>2</mtext>}}$ levels of cesium.     

Examination of vibration amplitude distribution of ultrasonic transducers using optical holography with a modulated reference beam

The theoretical base, experimental arrangement and results of the examination of the vibration amplitude distribution of ultrasonic transducers using an optical holography method with a reference beam whose frequency is shifted by the same amount as that of the vibrating object is presented. The thickness vibrations of transducers radiating into liquid in the frequency range 0.5 to 3 MHz have been examined.The minimum absolute value of displacement amplitude detected with this procedure is of the order 10^?9 m.     

Absorption line profile recovery based on residual amplitude modulation and first harmonic integration methods in photoacoustic gas sensing

Two methods for recovery of gas absorption line profiles are presented in this paper using photoacoustic spectroscopy and tunable diode laser spectroscopy (TDLS) with wavelength modulation (WM). A theoretical analysis based on Fourier coefficients is given in order to describe the various components that arise under simultaneous intensity and frequency modulation. The first method makes use of the residual amplitude modulation (RAM) signal which is always present in current modulation of distributed feedback (DFB) tunable diode lasers. The second method involves integration of a near-pure first harmonic derivative signal, separated from other distorting components by appropriate choice of the lock-in detection phase in the case of low modulation index. Good agreement is obtained with both methods between the experimental results and the theoretical simulation for the P17 absorption line of acetylene at 1535.39 nm but the second method gives a much improved accuracy and signal-to-noise ratio in lineshape recovery with photoacoustic spectroscopy.