Intensity of Cross-Peaks in Hyscore Spectra of S = 1/2, I = 1/2 Spin Systems

The cross-peak intensity for a S = 1/2, I = 1/2 spin system in two-dimensional HYSCORE spectra of single-crystals and powders is analyzed. There is a fundamental difference between these two cases. For single crystals, the cross-peak intensity is distributed between the two (+, +) and (+, −) quadrants of the hyperfine sublevel correlation (HYSCORE) spectrum by the ratio c²:s² (C. Gemperle, G. Aebli, A. Schweiger, and R. R. Ernst, J. Magn. Reson. 88, 241 (1990)). However, for powder spectra another factor becomes dominant and governs cross-peak intensities in the two quadrants. This factor is the phase interference between modulation from different orientations of the paramagnetic species. This can lead to essentially complete disappearance of the cross-peak in one of the two (+, +) or (+, −) quadrants. In the (+, +) quadrant, cross-peaks oriented parallel to the main (positive) diagonal of the HYSCORE spectrum are suppressed, while the opposite is true in the (+, −) quadrant where cross-peaks nearly perpendicular to the main (negative) diagonal of HYSCORE spectra are suppressed. Analytical expressions are derived for the cross-peak intensity profiles in powder HYSCORE spectra for both axial and nonaxial hyperfine interactions (HFI). The intensity is a product of two terms, one depending only on experimental parameter (τ) and the other only on the spin Hamiltonian. This separation provides a rapid way to choose τ for maximum cross-peak intensity in a region of interest in the spectrum. For axial HFI, the Hamiltonian-dependent term has only one maximum and decreases to zero at the canonical orientations. For nonaxial HFI, this term produces three separate ridges which outline the whole powder lineshape. These three ridges have the majority of the intensity in the HYSCORE spectrum. The intensity profile of each ridge resembles that observed for axial HFI. Each ridge defines two principal values of the HFI similar to the ridges from an axial HFI.     

Positron annihilation measurements across the superconducting transition in Y1Ba2Cu3O7−x

Positron lifetime and Doppler broadened annihilation radiation lineshape measurements have been carried out in Y₁Ba₂Cu₃O_7−x as a function of temperature in the range of 300 K to 58 K. The positron lifetime and the peak parameter of the annihilation radiation lineshape are observed to decrease on lowering the temperature without showing any discontinuous change across the superconducting transition temperature of 90 K as determined by susceptibility measurements. The variation of positron annihilation parameters with temperature in the superconducting state is significantly larger than that in the normal state. This is qualitatively explained in terms of the dimerization of oxygen ions in the superconducting state of Y₁Ba₂Cu₃O_7−x .     

Dynamic NMR: A new procedure for the estimation of mixing times in the 2D EXSY experiments. A four-site exchange system studied by 1D and 2D EXSY spectroscopy

A procedure for the estimation of the mixing time between the last two 90° pulses in the classic three-pulse sequence NOESY/EXSY is proposed and tested and some considerations for the treatment of the two-dimensional (2D) ¹H NMR exchange spectra are given. The rate constants are thus obtained with reasonable precision. This procedure was followed to obtain the 2D spectra of the model compound α-[bis(dimethylamino)methylene]-4-nitrophenylacetonitrile, which represents a four-site exchange system. The barriers to restricted rotations found in this compound were also determined from one-dimensional (1D) ¹H NMR spectra, which were processed with the iterative complete lineshape analysis (CLSA) method. The double-fit approach was incorporated in the CLSA method. It is shown that the results from the 2D dynamic NMR spectral studies corroborate those obtained by the CLSA double-fit method.     

Quantification of magnetic resonance spectroscopy signals with lineshape estimation

Quantification of magnetic resonance spectroscopy (MRS) signals is required for providing metabolite concentrations of the tissue under investigation. For estimating these concentrations several biochemical and acquisition conditions need to be taken into account. It is still a challenge to obtain reliable concentrations, as experimental conditions may have a detrimental effect on the spectral quality. The lineshape of MRS signals is affected, for instance, by inhomogeneities of the static magnetic field arising from imperfect shimming and tissue heterogeneities. To handle this type of distortions, we propose an extension of the self‐deconvolution method, where a common lineshape is estimated and a robust method with local regression is included to improve the smoothing of the estimated damping (or lineshape) function. This common lineshape is imposed in the metabolite quantification method and the spectral parameters (amplitude, frequency, damping and phase corrections) are obtained via nonlinear least squares. In this study, we considered distorted simulated, in vitro and in vivo rat brain signals which were lineshape corrected and quantitative results were compared in all three cases. Copyright © 2011 John Wiley & Sons, Ltd.     

电光调制器低频控制对受残余幅度调制影响的频率调制光谱线型优化研究

频率调制(FM)光谱技术中由于激光偏振态变化产生的残余幅度调制(RAM)使其在微量气体检测中的应用受到极大的限制。理论上详细分析了这一过程产生的原因,获得了存在RAM时FM光谱线型的表达式,同时给出N.C.Wong和J.L.Hall(W-H)方案抑制RAM后的FM光谱线型表达式;在实验上通过对乙炔气体的测量获得了存在RAM时的光谱线型,同时采用W-H方案对RAM进行了抑制,并获得了优化的光谱线型;最后基于理论结果对实验线型进行了拟合,两者差值小于信号峰峰值的4%。     

Air pressure broadening and shifting of high-J lines of (00011) ← (00001) band of CO2

The absorption spectra of carbon dioxide (isotope 626, natural abundance in air, ambient temperature) have been studied at total pressures 68-570 Torr with spectral resolution 0.003-0.005 cm⁻¹. The spectra were measured in the spectral domain of 2273-2393 cm⁻¹ by FTIR spectrometer Bruker IFS 125 HR equipped with White-type multipass cell (6.4-41.6 m) and with a cell having 10 cm optical path length. Pressure broadening and shift coefficients were obtained from a series of spectra by means of a nonlinear least-squares spectral fitting technique for the lines of the (00011)←(00001) band with rotational quantum number up to J=82. For fitting of the individual line shapes, we used the Voigt profile with pre-calculated Doppler broadening parameter. The experimental pressure broadening and shift coefficients are compared with the values available in spectroscopic databases HITRAN 2008 and Carbon Dioxide Spectroscopic Databank (CDSD-296) and with other experimental values reported in the literature.     

Room-temperature broadening and pressure-shift coefficients in the ν2 band of CH3D-O2: Measurements and semi-classical calculations

We report measured Lorentz O₂-broadening and O₂-induced pressure-shift coefficients of CH₃D in the ν₂ fundamental band. Using a multispectrum fitting technique we have analyzed 11 laboratory absorption spectra recorded at 0.011 cm⁻¹ resolution using the McMath-Pierce Fourier transform spectrometer, Kitt Peak, Arizona. Two absorption cells with path lengths of 10.2 and 25 cm were used to record the spectra. The total sample pressures ranged from 0.98 to 339.85 Torr with CH₃D volume mixing ratios of 0.012 in oxygen. We report measurements for O₂ pressure-broadening coefficients of 320 ν₂ transitions with quantum numbers as high as J″ = 17 and K = 14, where K″ = K′ ≡ K (for a parallel band). The measured O₂-broadening coefficients range from 0.0153 to 0.0645 cm⁻¹ atm⁻¹ at 296 K. All the measured pressure-shifts are negative. The reported O₂-induced pressure-shift coefficients vary from about −0.0017 to −0.0068 cm⁻¹ atm⁻¹. We have examined the dependence of the measured broadening and shift parameters on the J″, and K quantum numbers and also developed empirical expressions to describe the broadening coefficients in terms of m (m = −J″, J″, and J″ + 1 in the ^QP-, ^QQ-, and ^QR-branch, respectively) and K. On average, the empirical expressions reproduce the measured broadening coefficients to within 4.4%. The O₂-broadening and pressure shift coefficients were calculated on the basis of a semiclassical model of interacting linear molecules performed by considering in addition to the electrostatic contributions the atom-atom Lennard-Jones potential. The theoretical results of the broadening coefficients are generally larger than the experimental data. Using for the trajectory model an isotropic Lennard-Jones potential derived from molecular parameters instead of the spherical average of the atom-atom model, a better agreement is obtained with these data, especially for |m| ? 12 values (11.3% for the first calculation and 8.1% for the second calculation). The O₂-pressure shifts whose vibrational contribution are either derived from parameters fitted in the ^QQ-branch of self-induced shifts of CH₃D or those obtained from pressure shifts induced by Xe in the ν₃ band of CH₃D are in reasonable agreement with the scattered experimental data (17.0% for the first calculation and 18.7% for the second calculation).     

Fourier transform spectrometer instrument lineshape (ILS) retrieval by Fourier deconvolution

This work presents a Fourier deconvolution (FD) technique for retrieving the instrument lineshape (ILS) function of high-resolution Fourier transform infrared (FTIR) spectrometers. The ILS retrieved by FD is compared with the results obtained using the LINEFIT technique of Hase. The effect of a non-ideal ILS function on quantitative analysis of HBr is explored and improvements in the results of quantitative analyses are demonstrated.     

塞曼调制磁旋转光谱线型的研究

在研究塞曼调制磁旋转光谱线型的过程中，发现了入射光场的偏振特性地谱线型的影响，从而解释了实验中出现的各种线型，其中包括一些难以解释的除二次微分线型外的其它线型，并且在实验中，得到了理论分析一致的结果，为塞曼调制旋转光谱，激光光谱技术，光谱测量精度的进一步改善提供了参考依据。