Temperature coefficient of NH chemical shifts of thioamides and amides in relation to structure

NH chemical shift temperature coefficients have been measured in a large series of N-substituted-3-piperidinethiopropionamides in which the NN distances are short but of varied length, as well as in a couple of the corresponding amides and in some simpler amides and thioamides. Geometries are calculated by means of ab initio DFT methods. The N-substituted-3-piperidinethiopropionamides show in most cases strong intramolecular N–HN hydrogen bonds according to IR spectra and ab initio calculations. For compounds with rather short NN distances the S=C–N–H moiety is non-planar. Dihedral angles as small as 160° are found. The NH chemical shift coefficients measured in non-polar solvents in all the N-substituted-3-piperidinethiopropionamides are more negative (−8 to −17 ppb/K) than in non-hydrogen bonded thioamides. For the latter in non-polar solvents like CDCl₃ and toluene the temperature coefficients are as small as −1 to −4 ppb/K. The large negative effects can be related not only to the non-planarity of the thioamide group in a way that the more pronounced the non-planarity the more negative the temperature coefficients, but also to strong hydrogen bonding and the fact that the acceptor is a nitrogen. For similar amides with non-planar amide groups and nitrogen acceptor large negative temperature coefficients are likewise seen. In polar solvents like DMF the effects in simple thioamides are uniform and close to −6 ppb/K, whereas in the more complex compound like 4p(t) the temperature coefficient is close to 0. An essential feature of measuring temperature coefficients of compounds without strong intramolecular hydrogen bonds in non-polar solvents and at low temperatures is to keep the concentration low enough to avoid dimerisation.     

闪光照相条件下相对质量吸收系数的测量

 介绍了闪光照相中X光传播规律的等效单能模型。针对闪光照相出光重复性差、能谱测量困难的特点提出了相对质量吸收系数的概念。阐述了闪光照相中相对质量吸收系数的测量原理和方法。在闪光照相实验设备上采用整条D～L曲线对钨材料相对质量吸收系数进行了测量，得到的实验结果为1.23，与数值模拟结果1.26符合较好。     

KDP晶体三倍频实验和分析

报道了ＫＤＰ晶体中的三倍频产生的实验研究，计算了比较了直接三倍频过程和级联过程对ＫＤＰ晶体三阶有效非线性系数的贡献，并探讨了ＫＤＰ作为非线性晶体材料三阶非线性系数测量基准的可行性。     

Hilbert Space of Probability Density Functions Based on Aitchison Geometry

The set of probability functions is a convex subset of L1 and it does not have a linear space structure when using ordinary sum and multiplication by real constants. Moreover, difficulties arise when dealing with distances between densities. The crucial point is that usual distances are not invariant under relevant transformations of densities. To overcome these limitations, Aitchison＇s ideas on compositional data analysis are used, generalizing perturbation and power transformation, as well as the Aitchison inner product, to operations on probability density functions with support on a finite interval. With these operations at hand, it is shown that the set of bounded probability density functions on finite intervals is a pre-Hilbert space. A Hilbert space of densities, whose logarithm is square-integrable, is obtained as the natural completion of the pre-Hilbert space.     

线性常微分方程的保线性变换及其应用

研究了线性常微分方程的保线性变换，得到任意两个二阶线性常微分方程等价的条件，并用于求解一类二阶线性变系数齐次常微分方程．对数学物理方法教学中怎样通过适当的变换把给定的二阶线性变系数齐次常微分方程化为可解的方程给出了合理解释。     

Large deviation for the empirical eigenvalue density of truncated Haar unitary matrices

Let U_m be an m×m Haar unitary matrix and U_[m,n] be its n×n truncation. In this paper the large deviation is proven for the empirical eigenvalue density of U_[m,n] as m/n→λ and n→∞. The rate function and the limit distribution are given explicitly. U_[m,n] is the random matrix model of quq, where u is a Haar unitary in a finite von Neumann algebra, q is a certain projection and they are free. The limit distribution coincides with the Brown measure of the operator quq.     

Complex Geometry of the Universal Teichmuller Space

We prove that all invariant distances on the universal Teichmuller space agree and are determined by the Grunsky coefficients of the naturally related conformal maps. This fact yields various important consequences; in particular, we obtain solutions of certain well-known geometric problems in complex analysis and related fields.     

Unique continuation along curves and hypersurfaces for second order anisotropic hyperbolic systems with real analytic coefficients

In this paper we prove the following kind of unique continuation property. That is, the zero on each geodesic of the solution in a real analytic hypersurface for second order anisotropic hyperbolic systems with real analytic coefficients can be continued along this curve.

     

Ar-Broadening of isotropic Raman lines in the ν2 band of acetylene

Using a high resolution Raman spectrometer, we have measured Ar-broadening coefficients in the ν₂Q branch of C₂H₂ for 22 lines at 295 K, 20 lines at 174 K, and 16 lines at 134 K. These lines with J values ranging from 1 to 23 are located in the spectral range 1970.9-1974.3 cm⁻¹. The collisional widths are obtained by fitting each spectral line with a Rautian profile. The resulting broadening coefficients are compared with theoretical values arising from close coupling and coupled states calculations. A satisfactory agreement is obtained at room as well as at low temperatures, especially for odd J lines. By comparing broadening coefficients at 295, 174, and 134 K from a simple power law, the temperature dependence of these broadenings has been determined both experimentally, and theoretically.     

基于改进的语音参数提取的线性预测

根据语音发生基本原理和线性预测编码原理，针对自相关法需要加窗从而降低了解的精度，而协方差法不能保证保证解所重构出系统的稳定性的特点，提出了一种改进的Cholesky分解的方法求解协方差方程组以产生声道模型参数的方法，实践证明，这种方法既保证了系统的稳定性，又提高了解的精度。