活化LaNi5衍射峰各向异性应力展宽模型在LHPM程序中的实现

在活化LaNi5的粉末衍射轮廓中会出现较明显的各向异性展宽现象,这给衍射数据的Rietveld分析带来相当的难度.Rodriguez-Carvajal提出了一个唯像模型,只需精修少量的参数就能对于各向异性展宽的衍射峰获得较好的拟合.基于这个模型的原理,本文描述了活化laNi5衍射峰各向异性应力展宽模型在LHPM 6.5中的实现过程,并将所得结果与FullProf 2000的结果进行了比较.     

Semi-gas kinetics model for performance modeling of flowing chemical oxygen-iodine lasers (COIL)

The gas pressure in a laser cavity of flowing chemical oxygen-iodine laser (COIL)is about 133.31333 Pa[1]. In this pressure range, effects of homogeneous and inhomo-geneous broadening competing with each other on the performances of a COIL are no-ticeable. Generally, a rate equation (RE) model is adopted to the performance modeling of a supersonic COIL, such as in refs. [1—4]. This model assumes the spectral line pro-file is homogeneously broadened. Homogeneous broadening assumption sim…     

Band broadening evaluation by back-and-forth capillary electrophoresis

The purpose of this study is to develop a method for precise evaluation of band broadening in capillary electrophoresis. A capillary electrophoresis system with on-column twin detectors is constructed. Back-and-forth electrophoresis permits zones to make a round trip between the twin detectors placed at distant positions on the capillary. The system is capable of eliminating extra-column effects and discriminating between reversible and irreversible band-broadening mechanisms.     

Studies on external peak broadening in open-tubular liquid chromatography systems using the exponentially modified Gaussian model

Summary To optimize performance in Open-Tubular Liquid Chromatography (OTLC) it is necessary to minimize external peak broadening. To see how to reduce the external broadening an insight into its origins is required. This can be obtained by careful evaluation of experimental results with peak deconvolution methods based on the exponentially modified Gaussian model and comparison with theoretical predictions. It is assumed that the column response is Gaussian and that the responses due to the external effects are exponential.For peak deconvolution the algorithm described by Yau was used. Simulations were carried out to check the performance of the algorithm in calculating the standard deviation and the time constant. The effects of the presence of more than one time constant and of the number of data points and their position were investigated. The limits within which reliable results can be obtained are reported.Experimental results were obtained with laser-induced fluorescence and mass spectrometric detection. It is shown that the Yau algorithm can be used to obtain physically realistic estimates of the contribution to peak distortion in the various system components. By suitable design external effects can be reduced to the order of 1 nl and in some cases even lower limits can be reached.Part of this paper was presented at the 3rd Workshop on LC/MS and MS/MS, October, 24–26, 1984 in Montreux, Switzerland.     

Velocity autocorrelation function for the motion of long-chain molecules in the free draining limit

The thermal motion of a long-chain molecule dispersed in a solvent is examined in terms of the velocity autocorrelation, in a reference frame attached to a subunit of the chain.     

Amplified low-repetition-rate fs pulsewidth measuring and DLA caused pulse broadening

Amplified low-repetition-rate fs pulse is generated with dye laser amplifier(DLA). The pulsewidth is measured with a computer-aided autocorrelator and the fs pulsewidth broadening caused by the dispersion of the DLA is analyzed. Furthermore, the autocorrelator introduced in this paper could be used as a low scanning autocorrelator to measure high-repetition-rate pulsewidth.     

Pressure effect study on the I－V property of the GaAs-based resonant tunnelling structure by photoluminescence measurement

This paper discusses the I-V property of the GaAs-based resonant tunnelling structure （RTS） under external uniaxial pressure by photoluminescence studies. Compressive pressure parallel to the [110] direction, whose value is determined by Hooke＇s law, is imposed on the sample by a helix micrometer. With the increase of the applied external uniaxial compressive pressure, the blue shift and splitting of the luminescence peaks were observed, which have some influence on the I-V curve of RTS from the point of view of the energy gap, and the splitting became more apparent with applied pressure. Full width at half maximum broadening could also be observed.     

Linewidths of ammonia in collisions with He: Calculations from an ab initio potential

We present semiclassical calculations based on the Robert-Bonamy formalism of collisional broadening coefficients of ammonia by collision with He at room temperature. Calculations have been performed with the accurate ab initio potential of Hodges and Wheatley. The calculated line widths are compared to the available experimental data and a satisfactory agreement is found, although the model contains no adjustable parameters. However the calculations also exaggerate the K dependence of the broadenings, especially for lines with K = J − 1 or K = J.     

Cryogenic absorption cells operating inside a Bruker IFS-125HR: First results for CH4 at 7 μm

New absorption cells designed specifically to achieve stable temperatures down to 66 K inside the sample compartment of an evacuated Bruker IFS-125HR Fourier transform spectrometer (FTS) were developed at Connecticut College and tested at the Jet Propulsion Laboratory (JPL). The temperature stabilized cryogenic cells with path lengths of 24.29 and 20.38 cm were constructed of oxygen free high conductivity (OFHC) copper and fitted with wedged ZnSe windows using vacuum tight indium seals. In operation, the temperature-controlled cooling by a closed-cycle helium refrigerator achieved stability of ±0.01 K. The unwanted absorption features arising from cryodeposits on the cell windows at low temperatures were eliminated by building an internal vacuum shroud box around the cell which significantly minimized the growth of cryodeposits. The effects of vibrations from the closed-cycle helium refrigerator on the FTS spectra were characterized. Using this set up, several high-resolution spectra of methane isotopologues broadened with nitrogen were recorded in the 1200-1800 cm⁻¹ spectral region at various sample temperatures between 79.5 and 296 K. Such data are needed to characterize the temperature dependence of spectral line shapes at low temperatures for remote sensing of outer planets and their moons. Initial analysis of a limited number of spectra in the region of the R(2) manifold of the ν₄ fundamental band of ¹³CH₄ indicated that an empirical power law used for the temperature dependence of the N₂-broadened line widths would fail to fit the observed data in the entire temperature range from 80 to 296 K; instead, it follows a temperature-dependence similar to that reported by Mondelain et al. [17] and [18]. The initial test was very successful proving that a high precision Fourier transform spectrometer with a completely evacuated optical path can be configured for spectroscopic studies at low temperatures relevant to the planetary atmospheres.     

On the accuracy of classical, semiclassical and quantum methods in collision line broadening calculations: Comparative analysis for C2H2-Ar, He systems

Accuracies of classical, semiclassical and quantum methods are comprehensively examined in calculations of impact line widths of C₂H₂ molecules perturbed by Ar and He. The field of comparative study covers both infrared absorption and Raman scattering lines of acetylene having rotational quantum number J=0-30 at temperatures 173 and 296 K. Calculations have been made by fully classical method and by three basic least approximate semiclassical methods, namely, Neilsen-Gordon (NG) method, peaking approximation (PA) and Smith-Giraud-Cooper (SGC) method. Most accurate ab initio potential energy surfaces (PES) of Yang et al. (1996) [21] and Mozsynski et al. (1995) [22] have been applied to model C₂H₂-Ar and C₂H₂-He interactions. The comparison has been made also with available experimental data and with the results of rigorous fully quantum-mechanical calculations within close coupling and coupled states approaches in identical conditions. Semiclassical methods are proved to be not so much accurate as it is generally believed since all they gave in the cases considered seriously underestimated results. The fundamental issue of the adequacy of simplified trajectories in collision broadening calculations is finally reasonably solved. In cases of C₂H₂-Ar and C₂H₂-He systems the use of the “exact” isotropic trajectories (i.e. driven only by the isotropic part of PES) is the main reason of failing of NG, PA and SGC methods. Thus the neglecting of back-influence of the RT exchange on the classical path is a principal defect of semiclassical methods. Finally, the application of simplified trajectories is recognized as inadequate and risky in broadening calculations for molecules having relatively small rotational constants when accurate ab initio PES are applied.