Lineshapes of spin exchange broadened EPR spectra

An unexplained residual in the fits of theoretical and experimental spectra of exchange broadened nitroxide spin probes reported by Robinson et al. [J. Magn. Reson. 138 (1999) 199] is shown to be understood by inclusion of theoretically predicted lineshape changes into the fitting routine. These lineshape changes provide an additional estimate of the spin exchange frequency that is independent of linewidth methods.     

Selective inversion in inhomogeneously broadened powder spectra

It is shown how amplitude-modulated radio-frequency pulses optimized for selective inversion of magnetization can be applied to static powder samples with inhomogeneously broadened spectra. Selective one-dimensional methods can in principle provide information similar to two-dimensional exchange spectroscopy, and they are often more efficient for determining the rates of dynamic processes. However, in systems where transverse magnetization is subject to significant homogeneous decay during the rf pulses, selective one-dimensional methods do not necessarily offer the expected advantages over two-dimensional spectroscopy.     

On the lineshape of spin-relaxation broadened Mössbauer spectra of some Fe3+ paramagnets

The spin relaxation broadened Mössbauer spectra of alums and Fe(NO₃)₃·9H₂O were studied. A correlation between the different types (α, β) of alums and the characteristics of the spin relaxation has been found.     

Diode laser measurements of the first overtone HF lineshape broadened by Ar,Xe, Kr and N2

A high-resolution spectroscopy study of the HF first overtone vibrational–rotational 0–2 R(0) line profile was carried out in Ar, Xe, Kr and N₂ gas mixtures using near-IR tunable diode laser. The HF 0–2 R(0) analytical line is known as the most appropriate for laser detection of HF molecules in the atmosphere. Highly accurate collisional broadening, shift and “narrowing” coefficients were determined from the direct spectroscopic fit employing traditional Voigt, Rautian and Galatry symmetric profiles and using an asymmetric speed-dependent Voigt profile. These data make the information of modern spectroscopic databases, e.g., HITRAN2012, much more exact. A noticeable line shape asymmetry was investigated in detail. In this paper, the validity of the use of model profiles in spectroscopic fitting is severely discussed. For the first time, we draw attention to the need for physically realistic line shape models to avoid systematic errors in retrieved gas concentrations. We stress that in the case of HF, all considered model profiles serve only as ad hoc models; they may conceal the true physics of spectral line formation.     

Application of magnetic field over-modulation for improved EPR linewidth measurements using probes with Lorentzian lineshape

Magnetic field modulation in CW electron paramagnetic resonance (EPR) is used for signal detection. However, it can also distort signal lineshape. In experiments where the linewidth information is of particular importance, small modulation amplitude is usually used to limit the lineshape distortion. The use of small modulation amplitude, however, results in low signal-to-noise ratio and therefore affects the precision of linewidth measurements. Recently, a new spectral simulation model has been developed enabling accurate fitting of modulation-broadened EPR spectra in liquids. Since the use of large modulation amplitude (over-modulation) can significantly enhance the EPR signal, the precision of linewidth measurements is therefore greatly improved. We investigated the over-modulation technique in EPR oximetry experiments using the oxygen-sensing probe lithium octa-n-butoxy-substitued naphthalocyanine (LiNc-BuO). Modulation amplitudes 2-18 times the intrinsic linewidth of the probe were applied to increase the spectral signal-to-noise ratio. The intrinsic linewidth of the probe at different oxygen concentrations was accurately extracted through curve fitting from the enhanced spectra. Thus, we demonstrated that the over-modulation model is also applicable to particulate oxygen-sensing probes such as LiNc-BuO and that the lineshape broadening induced by oxygen is separable from that induced by over-modulation. Therefore, the over-modulation technique can be used to enhance sensitivity and improve linewidth measurements for EPR oximetry with particulate oxygen-sensing probes with Lorentzian lineshape. It should be particularly useful for in vivo oxygen measurements, in which direct linewidth measurements may not be feasible due to inadequate signal-to-noise ratio.     

A statistical theory for powder EPR in distributed systems

A statistical interpretation is presented for “g strain,” the dominant broadening in the EPR spectra of metallo-proteins. The direct cause of g strain is described by a three-dimensional tensor p, whose principal elements are random variables. The p and g tensors are not necessarily colinear. The observed EPR linewidth results from a distribution in the effective g value as a function of (a) the joint distribution function of the elements of the p tensor and (b) the spatial relationship between the two principal axis systems involved. The theory is reformulated in terms of matrices that facilitate a direct comparison with earlier work. Two previous theories of g strain represent different subsets of the general theory, namely, the case of zero rotation between axis systems and the case with nonzero rotation and full correlation between elements of the p tensor.     

EPR lineshape study of the incommensurate phase in γ-irradiated K2SeO4

The temperature dependence of the SeO^4-₄ EPR frequencies and the asymmetric broadening of the EPR lines in the incommensurate phase of K₂SeO₄ can be explained by an incommensurate spatial modulation of the g tensors which corresponds to the “broad” phase soliton limit. A comparison between the experimental and calculated lineshape shows a ≈1% volume fraction of commensurate regions in the middle of the incommensurate phase at 110 K.     

EPR study of table sugar rod and powder as high dose dosimeters

In order to improve the ease of sample handling, the reproducibility of signal detection and quantification, simple methods of incorporating a homogeneous mixture containing sugar powder (30%) with wax (35%) and rubber (35%) into rods has been adopted. The dose response, the time stability of the free radicals produced in table sugar dosimeters (in both rod and powder form) by gamma radiation and the effect of the temperature during irradiation were studied by EPR (Electron Paramagnetic Resonance). The peak-to-peak height (PPH) measurement of the EPR signal is studied as a function of the absorbed gamma dose in the range 0.1–58 kGy. For the two forms, a linear dependency is found between 0.1 and 26 kGy. At higher doses the EPR signal amplitude continues to grow but non-linear up to 58 kGy. The dependence of temperature during irradiation has been investigated in the temperature range 25–40 °C and the calculated correction coefficients were found (2.7 ± 0.2)% °C^?1 and (1.5 ± 0.3)% °C^?1, respectively, for powder and rod forms. The time stability of the stored sugar samples was investigated for 34 days at room temperature, a rapid decrease of EPR signal was showed immediately after irradiation followed by slowly decrease.     

非均匀加宽单模激光器的最佳透射率

给出四能级系统非均匀加宽单模激光器最佳透射率的表达式和分布曲线,并与均匀加宽单模激光器最佳透射率进行了比较.叙述了非均匀加宽单模激光器的特点.     

Measurement of stark broadened Lyman-lines

Stark broadened profiles of the hydrogen Lyman-lines Ly-α to Ly-? have been measured in a wall-stabilized argon arc, providing a plasma of an electron density of 7·2 X 10¹⁶ cm^-3 and a temperature of 12,200 K. In the cases of Ly-α and Ly-β, detailed investigations of the profiles are performed including absolute measurements, measurements of line shifts and asymmetries and comparisons with modern theories. Moreover, a comprehensive discussion of experimental errors is given and some important features of the radiation source are outlined.     

非均匀偏振光场的应力工程及应用

光场偏振态的空间不均匀性对光束聚焦、传播、照明、成像等方面具有奇异的效应。本文将举例说明在光学元件的外周施加确定的应力可以用于对波束传播的基本特性的研究,而且还能获得一些应用,比如旋光器件等。     

N-dependence of the lineshape in nonlinear radiation phenomena

Preliminary experimental results are reported on the investigation of the dependence of the intensity of the second harmonic generated by paramagnets on the number N of spins. A qualitative argument in terms of correlation effects among the spins is tentatively put forward to interpret the results.     

A note on FMR lineshape of conductive spheres

A shoulder-shaped anomaly on the high-field side of the main FMR maximum has been re-examined in connection with a recent publication on FMR in ferromagnetic semiconductors. The positions of the shoulder are measured at 9.3 and 14.8 GHz for different values of resistivities, magnetization and sphere sizes. Results clarify the role of the surface and volume type excitations in the occurrence of the shoulder.     

Spectroscopic lineshape study of the self-perturbed oxygen A-band

This paper reports accurate line positions, intensities, self-broadening, -shift and -line mixing coefficients for 56 rotational transitions from multispectrum fits of low noise, high-resolution Fourier-transform spectra. The measured line intensities are within the statistical spread of the previous measurements available in the literature—thus contributing to the efforts to measure the oxygen A-band intensities with an accuracy better than 1%. We determined the integrated band strength and Einstein A coefficient. Using our spectrum calibration method we could clearly show for the first time that there is a meaningful statistical discrepancy in the frequency standards used in spectroscopic studies for the oxygen A-band. We were able to explain how this discrepancy leads to two different sets of shifts reported in the literature and demonstrate the need for precise frequency-type transition wavenumber measurements of the oxygen A-band transitions. We observed deviations from the conventional Voigt profile due to speed-dependent broadening and line mixing effects. Dicke narrowing was observed on a selected group of spectra recorded at pressures between 98 and 337 Torr. The Dicke narrowed lineshapes were best modeled using a Galatry profile implemented using a fixed value for the velocity-changing collision rate. The weak line mixing coefficients were determined from fits using the speed-dependent models. Exponential Power Gap (EPG) and Energy Corrected Sudden (ECS) scaling laws were used to calculate the self-broadening and self-line mixing coefficients.