分析化学教材中关于离子活度系数计算公式的讨论

在处理电解质溶液的化学平衡理论中,有关离子的活度和活度系数的计算或估算都有比较严谨的理论公式或经验公式,而国内分析化学教材中关于经验公式的表述略显随意。以0.050 mol·L^-1AlCl₃水溶液中Cl^-和Al³⁺的活度计算为例,结合国内外分析化学教材中关于活度系数计算的经验公式进行讨论。由计算结果可知,关于活度系数计算的经验公式需给出明确的使用条件。     

Heavy‐Atom Tunneling Calculations in Thirteen Organic Reactions: Tunneling Contributions are Substantial,and Bell's Formula Closely Approximates Multidimensional Tunneling at ≥250 K

Multidimensional tunneling calculations are carried out for 13 reactions, to test the scope of heavy‐atom tunneling in organic chemistry, and to check the accuracy of one‐dimensional tunneling models. The reactions include pericyclic, cycloaromatization, radical cyclization and ring opening, and S_N2. When compared at the temperatures that give the same effective rate constant of 3×10⁻⁵ s⁻¹, tunneling accounts for 25–95 % of the rate in 8 of the 13 reactions. Values of transmission coefficients predicted by Bell's formula, κ_Bell , agree well with multidimensional tunneling (canonical variational transition state theory with small curvature tunneling), κ_SCT. Mean unsigned deviations of κ_Bell vs. κ_SCT are 0.08, 0.04, 0.02 at 250, 300 and 400 K. This suggests that κ_Bell is a useful first choice for predicting transmission coefficients in heavy‐atom tunnelling.     

On the order of summability of the Fourier inversion formula

In this article we show that the order of the point value, in the sense of Łojasiewicz, of a tempered distribution and the order of summability of the pointwise Fourier inversion formula are closely related. Assuming that the order of the point values and certain order of growth at infinity are given for a tempered distribution, we estimate the order of summability of the Fourier inversion formula. For Fourier series, and in other cases, it is shown that if the distribution has a distributional point value of order k, then its Fourier series is e.v. Cesàro summable to the distributional point value of order k+1. Conversely, we also show that if the pointwise Fourier inversion formula is e.v. Cesàro summable of order k, then the distribution is the (k+1)-th derivative of a locally integrable function, and the distribution has a distributional point value of order k+2. We also establish connections between orders of summability and local behavior for other Fourier inversion problems.     

自然数幂方和用二项系数表示的系数公式

得到了自然数幂方和由二项系数表示的系数a_i~(k)的公式,和由排列数表示的系数b_i~(k)的公式,证明了系数存在唯一性及系数间的若干重要性质,给出了计算系数的C-语言程序.     

A study of time over threshold (TOT) technique for plastic scintillator counter

A new charge measurement method, time over threshold (TOT), has been used in some gas detectors lately. Here TOT is studied for TOF system, made of plastic scintillator counter, which can simplify the electronics of the system. The signal characteristics are measured and analyzed with a high quality oscilloscope, including noise, pedestal, signal amplitude, total charge, rise time and the correlation between them. The TOT and charge are related and can be fitted by some empirical formula. The charge measurement resolution by TOT is given and this will help the design of TOF electronics.     

The Campbell- Hausdorff Series of Local Analytic Bruck Loops

The class of local analyitic Bruck loops (or equivalently K-loops) is strongly related to locally symmetric spaces. In particular, both have Lie triple systems as their tangent algebra. In this paper, we consider the existence and some properties of the Campbell-Hausdorff series of local analytic Bruck loops (K-loops). This formula can be used to determine the local symmetries of the associated symmetric space.     

Surface Measures and Tightness of (r,p)-Capacities on Poisson Space

We prove tightness of (r,p)-Sobolev capacities on configuration spaces equipped with Poisson measure. By using this result we construct surface measures on configuration spaces in the spirit of the Malliavin calculus. A related Gauss-Ostrogradskii formula is obtained.     

Estimation of the Density of Hypoelliptic Diffusion Processes with Application to an Extended Itô's Formula

We prove a uniform bound for the density, p _t (x), of the solution at time t(0, 1] of a 1-dimensional stochastic differential equation, under hypoellipticity conditions. A similar bound is obtained for an expression involving the distributional derivative (with respect to x) of p _t (x). These results are applied to extend the Itô formula to the composition of a function (satisfying slight regularity conditions) with a hypoelliptic diffusion process in the spirit of the work of Föllmer et al. ⁽⁵⁾