Line-shifting method in electron spin echo envelope modulation (ESEEM) studies

A novel line-shifting method, which is called mixing-frequency electron spin echo envelope modulation (MIF-ESEEM) spectroscopy, is introduced and analysed. It is shown that the spectral resolution is enhanced, and thus the overlapping is removed with this new method. The application of this method to systems withS≥1 andI≥1 is also discussed.     

Analyse du codage de l'information en tomographie longitudinale a haute resolution

Using a 3-D Fourier analysis, we investigate the nature of the informations contained in the high resolution motion pinhole recordings. We show that these images can be interpreted as parallel projections of a distorted 3-D emitting object. Thus, the use of the 3-D central slice theorem and the circular motion of the pinhole show that a 3-D Fourier region remains unexplored. Such a fact leads to a notable degradation of objects containing only very low spatial frequencies. But, in other cases, this degradation is generally less important (heart imaging for instance) and the improvement in resolution of this method proves to be appreciable when analysing local defects of fixation in nuclear medicine.     

Resolving ambiguities in two-dimensional NMR spectra: the 'TILT' experiment

Ambiguities in two-dimensional nuclear magnetic resonance spectra due to overlap are usually resolved by recording a three-dimensional version of the experiment. It is shown that a simpler solution is to record a tilted projection of the three-dimensional spectrum, derived by Fourier transformation of the time-domain signal acquired while the two evolution parameters are varied simultaneously at the appropriate rates. By avoiding the need to record the full three-dimensional spectrum, this saves an order of magnitude in measurement time. The tilt technique is illustrated by reference to degenerate responses in the TOCSY and NOESY spectra of a small protein, agitoxin, where the 1H and 15N frequencies are incremented in tandem.     

Application of two-dimensional pulsed EPR nutation spectroscopy to a disordered system with largeg-anisotropy

Two-dimensional (2-D) pulsed electron paramagnetic resonance (EPR) nutation spectroscopy is applied to a disordered system with strongly anisotropicg-factors. The analysis and interpretation of a 2-D nutation spectrum is performed by theoretical calculations appropriate for ferric myoglobin cyanide in frozen solution. The observed and calculated 2-D spectra show broad signals which correspond to the principalg-values. The advantage of nutation spectroscopy is demonstrated by measuring theg _x=0.93 signal, which cannot be observed in a conventional field-swept spectrum due to largeg strain broadening. It is shown that the 2-D nutation experiment can be considered as a sort of an angle-selected method but a nutation spectrum gives a powder pattern even for magnetic field settings at extreme field values of an EPR spectrum. This is in contrast to angle-selected electron nuclear double resonance, which gives a single-crystal type spectrum. The advantage of sine Fourier transform (FT) over complex FT is demonstrated for data processing in the nutation domain. Problems of experimental and data-processing procedures are also discussed.     

Comparison of some resolution enhancement methods applied to35Cl-NQR nutation spectroscopy

The³⁵Cl nuclear quadrupole resonance spin echo nutation spectroscopy method was used to determine asymmetry parameters,η, of the electric field gradient tensor in cyanuric chloride, 1,3,5-trichloro-cyanuric acid and 1,3-dichloro-5,5-dimethylhydantoin. For comparison of advantages and drawbacks of some data processing methods we have tried integral transforms of nutation interferogram (pseudo-FID) data (Hankel and Hartley transforms) alternative to the Fourier transform. Another processing method, which provides a power spectrum estimated from time-domain data, is the maximum entropy method (MEM), and we applied the Burg algorithm version of it. We found that MEM gives the best enhancement of the nutation spectrum resolution and the signal-to-noise ratio, provided the number of autocorrelation coefficients is chosen for optimum performance of the Burg algorithm, otherwise estimated singularities in the nutation spectrum can be obscured by multiple spurious peaks or the spectrum resolution is low. In the Hankel transform with the first-order Bessel functions the improvement in resolution is achieved at the expense of the overall signal-to-noise ratio and for noisy experimental data this transform did not show reliable results. The Hartley transform gives a resolution better than the Fourier transform but worse than the two other methods. Unlike the Hankel transform after the Hartley transform the signal-to-noise ratio is not degraded. Theη parameter determined by MEM for cyanuric chloride was 18%, which is close to previously reported values. For 1,3,5-trichloro-cyanuric acidη = 20% and for the two chlorine sites in 1,3-dichloro-5,5-dimethylhydantoinη = 0 and 12% respectively. These values are in substantial agreement with the anticipated double bond character of N-Cl bonds in the two last compounds.     

Analysis of the Structure of the Bands in the IR Spectrum of β-D Glucose by the Regularized Method of Deconvolution

Deconvolution of the IR absorption spectrum of -D glucose in the spectral range 1500–450 cm^–1 has been carried out. The results of the deconvolution were compared with the IR and Raman spectra recorded at room and low temperatures and with the data obtained by theoretical calculations for the frequencies of the normal vibrations of the -D glucose molecule in the crystalline state. It is shown that deconvolution of the IR spectra recorded at room temperature makes it possible to separate the bands observed experimentally only at a very low temperature of the sample and a number of components that were not resolved earlier. The number of bands separated on deconvolution of the IR spectra of -D glucose in the spectral range 1500–450 cm^–1 is more than twice the number of visible absorption maxima in the usual spectrum. The results of deconvolution of the IR spectrum of -D glucose are in good agreement with the data of theoretical calculations for the frequencies of the normal vibrations of the -D glucose molecule in the crystalline state. The existence of the factor-group (Davydov) splitting of a number of frequencies of the nondegenerate fundamental vibrations of molecules in a crystal cell has been revealed in the IR spectrum of -D glucose. It was concluded that the model of an isolated molecule is insufficient for detailed theoretical interpretation of the vibrational spectra of carbohydrates.     

超快太赫兹时域光谱系统

超快太赫兹时域光谱系统是基于高速异步光学采样原理进行工作的,该系统使用2个重复频率可在1 GHz附近变化的飞秒振荡器,并使用高带宽反馈电路控制其重复频率。2个飞秒振荡器的重复频率存在Δf的失谐,一个飞秒振荡器的重复频率是1 GHz+Δf Hz,为泵浦脉冲;另一个飞秒振荡器的重复频率是1 GHz,为探测脉冲,由此提供泵浦脉冲和探针脉冲的时间差,时间延迟呈周期性变化,其扫描周期可以由1/Δf给出。此系统摒弃了传统THz-TDS系统所必需的机械延迟线,采用双光子探测器来产生触发信号。当设定Δf=1 kHz时,1 ms就可以探测出1个THz谱, 用时10.3 s即可得到动态范围为21 dB、频谱分辨率为5 GHz的太赫兹信号。该系统具有检测速度快和频谱分辨率高的优点,在需要快速测量的应用环境中有着传统太赫兹时域光谱系统不可比拟的优势。     

Recording 2-D Nutation NQR Spectra by Random Sampling Method

The method of random sampling was introduced for the first time in the nutation nuclear quadrupole resonance (NQR) spectroscopy where the nutation spectra show characteristic singularities in the form of shoulders. The analytic formulae for complex two-dimensional (2-D) nutation NQR spectra (I = 3/2) were obtained and the condition for resolving the spectral singularities for small values of an asymmetry parameter η was determined. Our results show that the method of random sampling of a nutation interferogram allows significant reduction of time required to perform a 2-D nutation experiment and does not worsen the spectral resolution.     

STUDY OF MILLIMETER-WAVE WAVEGUIDES USING A 2-D ORDER-MARCHING TIME-DOMAIN METHOD

In this paper, the application of the order-marching time-domain (OMTD) method to the solution of the cutoff frequencies of TE and TM modes in millimeter-wave waveguides is described. Starting from Maxwell’s two-dimensional (2-D) differential equations for TE or TM case, the OMTD method uses the orthonormality of weighted Laguerre polynomials and Galerkin’s testing procedure to eliminate the temporal variables and results in an order-marching scheme. To verify it’s accuracy and efficiency, the numerical results for millimeter-wave guided systems are compared with those of finite-difference time-domain (FDTD) method and analytical solutions. The OMTD method improves computational efficiency notably, especially for fine grid division problems restricted by stability constraints in the FDTD method. This work was supported by the National Natural Science Foundation of China (No. 60371008) and the CRT Program of UESTC.     

Studying the regime of complete decoupling of the bond between the electron and nuclear moments at the <Emphasis Type="Italic">D</Emphasis><Subscript>1</Subscript>-line of the <Superscript>39</Superscript>K potassium isotope using a spectroscopic microcell

Atomic transitions of the ³⁹K potassium isotope in strong (up to 1 kG) longitudinal and transverse magnetic fields have been studied with a high spectral resolution. It has been shown that crossover resonances are almost absent in the saturated absorption spectrum of potassium vapors in a 30-μm-thick microcell. This, together with the small spectral width of atomic transitions (~30 MHz), allows one to use the saturated absorption spectrum for determining frequencies and probabilities of individual transitions. Among the alkali metals, potassium atoms have the smallest magnitude of the hyperfine splitting of the lower level. This allows one to observe the break of the coupling between the electronic and nuclear angular momentums at comparatively low magnetic fields B > 500 G, i.e., to implement the hyperfine Paschen–Back regime (HPB). In the HPB regime, four equidistantly positioned transitions with the same amplitude are detected in circularly polarized light (σ⁺). In linearly polarized light (π) at the transverse orientation of the magnetic field, the spectrum consists of eight lines which are grouped in two groups each of which consists of four lines. Each group has a special distinguished G-transition and the transition that is forbidden in the zero magnetic field. In the HPB regime, the probabilities of transitions in a group and derivatives of their frequency shifts with respect to the magnetic field asymptotically tend to magnitudes that are typical for the aforesaid distinguished G-transition. Some practical applications for the used microcell are mentioned.     

基于自准直效应的Fabry-Perot干涉仪的设计

报道了基于圆柱型光子晶体自准直效应的低功耗Fabry-Perot干涉仪。该干涉仪是在二维光子晶体中引入两排线缺陷构成的。引入的线缺陷具有高反射率和低透射率。在自准直频率范围0.187c/a~0.201c/a,线缺陷的透射率介于20.77%~40.65%。利用时域有限差分方法对FPI的透射谱进行研究,结果表明对两排缺陷的间距d即使进行微小的扩大也会引起透射峰向低频移动,透射谱的自由光谱范围和透射峰的频率随着d的增大而变小,透射谱的半高宽会随着线缺陷的反射率的提高而逐渐变小。     

基于经验模态分解提高太赫兹频率分辨率的方法

太赫兹频率分辨率是影响物质鉴别的重要因素,但是由于太赫兹时域光谱系统中存在器件反射,使得参考信号和测量信号出现多个反射峰,时域信号长度截断导致频率分辨率很低。为了去除反射峰的影响,提出基于经验模态分解去除时域反射峰,从而提高太赫兹频率分辨率的方法。通过与太赫兹主峰的互相关定位时域反射峰,计算反射峰的上下包络和求平均值,获取本征模函数并代替反射峰,增加时域信号有效长度,提高太赫兹频域分辨率。空气中水蒸汽的太赫兹透射谱实验结果表明,该方法具有自适应去除多个反射峰的能力,对太赫兹时域信号修复效果良好,频率分辨率提高了12倍,而且未丢失有用的吸收谱信息,吸收峰的位置和个数与真实谱一致,很好地保留了太赫兹谱的鉴别能力。     

Performance studies on high pressure 1-D position sensitive neutron detectors

The powder diffractometer and Hi-Q diffractometer at Dhruva reactor make use of five identical 1-D position sensitive detectors (PSDs) to scan scattering angles in the range 3° to 140°. In order to improve the overall throughput of these spectrometers, it is planned to install a bank of 15 high-efficiency and high-resolution PSDs arranged in three layers with five PSDs in each layer. With each high pressure PSD (³He 10 bar + Kr 2 bar) showing the efficiency gain of 1.8 at 1.2 Å, detector bank is expected to show overall gain of 5.5 times the present detection efficiency and reduction in data collection time by equivalent factor. The 1-D PSDs are developed in batches of five, and are characterized so that all PSDs operate at uniform parameters such as position resolution, uniformity of efficiency and linearity of response. Position spectrum indicates the differential position resolution to be ～1 mm and integral position resolution to be 3–4 mm. Broadening of position spectrum at the extreme end of sensitive length of PSD is analysed using fine shift of the beam. Dependence of position resolution and dynamic range of output pulse on the input impedance of pre-amplifier is also presented.     

Resolution and uncertainty of Laplace inversion spectrum

Laplace inversion has been widely used in analyzing nuclear magnetic resonance data to obtain a spectrum of decay time constant, such as the T(2) spectrum. However, due to the ill-conditioned nature of such inversion, it is difficult to determine the reliability and error of the resulting spectrum. This article describes methods used to analyze resolution and to obtain bounds of integral quantities of the spectrum.     

Time-domain mid-infrared frequency-comb spectrometer

A novel type of Fourier-transform infrared spectrometer (FTIR) is demonstrated. It is based on two Ti:sapphire lasers emitting femtosecond pulse trains with slightly different repetition frequencies. Two mid-infrared beams-derived from those lasers by rectification in GaSe-are superimposed upon a detector to produce purely time-domain interferograms that encode the infrared spectrum. The advantages of this spectrometer compared with the common FTIR include ease of operation (no moving parts), speed of acquisition (100 micros demonstrated), and not-yet-shown collimated long-distance propagation, diffraction-limited microscopic probing, and electronically controllable chemometric factoring. Extending time-domain frequency-comb spectroscopy to lower (terahertz) or higher (visible, ultraviolet) frequencies should be feasible.     

The Length of an SLE—Monte Carlo Studies

The scaling limits of a variety of critical two-dimensional lattice models are equal to the Schramm–Loewner evolution (SLE) for a suitable value of the parameter κ. These lattice models have a natural parametrization of their random curves given by the length of the curve. This parametrization (with suitable scaling) should provide a natural parametrization for the curves in the scaling limit. We conjecture that this parametrization is also given by a type of fractal variation along the curve, and present Monte Carlo simulations to support this conjecture. Then we show by simulations that if this fractal variation is used to parametrize the SLE, then the parametrized curves have the same distribution as the curves in the scaling limit of the lattice models with their natural parametrization.     

Selective averaging for high-resolution solid-state NMR spectroscopy of aligned samples

Solid-state NMR experiments benefit from being performed at high fields, and this is essential in order to obtain spectra with the resolution and sensitivity required for applications to protein structure determination in aligned samples. Since the amount of rf power that can be applied is limited, especially for aqueous protein samples, the most important pulse sequences suffer from bandwidth limitations resulting from the same spread in chemical shift frequencies that aids resolution. SAMPI4 is a pulse sequence that addresses these limitations. It yields separated local field spectra with narrower and more uniform linewidths over the entire spectrum than the currently used PISEMA and SAMMY experiments. In addition, it is much easier to set up on commercial spectrometers and can be incorporated as a building block into other multidimensional pulse sequences. This is illustrated with a two-dimensional HETCOR experiment, where it is crucial to transfer polarization from the amide protons to their directly bonded nitrogens over a wide range of chemical shift frequencies. A quantum-mechanical treatment of the spin Hamiltonians under high-power rf pulses is presented which gives the scaling factor for SAMPI4 as well as the durations of the rf pulses to achieve optimal decoupling.     

Using wavelets to decompose the time-frequency effects of monetary policy

Central banks have different objectives in the short and long run. Governments operate simultaneously at different timescales. Many economic processes are the result of the actions of several agents, who have different term objectives. Therefore, a macroeconomic time series is a combination of components operating on different frequencies. Several questions about economic time series are connected to the understanding of the behavior of key variables at different frequencies over time, but this type of information is difficult to uncover using pure time-domain or pure frequency-domain methods.To our knowledge, for the first time in an economic setup, we use cross-wavelet tools to show that the relation between monetary policy variables and macroeconomic variables has changed and evolved with time. These changes are not homogeneous across the different frequencies.     

<Superscript>1</Superscript>H and<Superscript>13</Superscript>C chemical shift assignments and stereochemistry of matrine and oxymatrine

Matrine and oxymatrine were extracted fromSophora flavescens, and their¹H and¹³C nuclear magnetic resonances (NMR) were unambiguously assigned by a combination of different two-dimensional 2-D¹H-¹³C and¹H-¹H correlation experiments of HMQC, HMQC-TOCSY and MAXY. The technique of using those experiments to make the assignment of the heavily overlapped spectrum is demonstrated. The coupling constants of matrine were measured by 2-DJ-resolved spectrum and 1-D spectra extracted from the slices of 2-D MAXY spectrum. The stereochemistry of the titled compounds was established from the NMR spectroscopy.     

Pure-exchange solid-state NMR

Three exchange nuclear magnetic resonance (NMR) techniques are presented that yield (13)C NMR spectra exclusively of slowly reorienting segments, suppressing the often dominant signals of immobile components. The first technique eliminates the diagonal ridge that usually dominates two-dimensional (2D) exchange NMR spectra and that makes it hard to detect the broad and low off-diagonal exchange patterns. A modulation of the 2D exchange spectrum by the sine-square of a factor which is proportional to the difference between evolution and detection frequencies is generated by fixed additional evolution and detection periods of duration tau, yielding a 2D pure-exchange (PUREX) spectrum. Smooth off-diagonal intensity is obtained by systematically incrementing tau and summing up the resulting spectra. The related second technique yields a static one-dimensional (1D) spectrum selectively of the exchanging site(s), which can thus be identified. Efficient detection of previously almost unobservable slow motions in a semicrystalline polymer is demonstrated. The third approach, a 1D pure-exchange experiment under magic-angle spinning, is an extension of the exchange-induced sideband (EIS) method. A TOSS (total suppression of sidebands) spectrum obtained after the same number of pulses and delays, with a simple swap of z periods, is subtracted from the EIS spectrum, leaving only the exchange-induced sidebands and a strong, easily detected centerband of the mobile site(s).