Theoretical Study of Isomerization and Decomposition Reactions for Methyl-nitramine

The complex potential energy surface and reaction mechanisms for the unimolecular isomerization and decomposition of methyl-nitramine (CH3NHNO2) were theoretically probed at the QCISD(T)/6-311+G*//B3LYP/6-311+G* level of theory. The results demonstrated that there are four low-lying energy channels: (i) the NN bond fission pathway; (ii) a sequence of isomerization reactions via CH3NN(OH)O; (IS2a); (iii) the HONO elimination pathway; (iv) the isomerization and the dissociation reactions via CH3NHONO (IS3). The rate constants of each initial step (rate-determining step) for these channels were calculated using the canonical transition state theory. The Arrhenius expressions of the channels over the temperature range 298-2000 K are k6(T)=1014:8e-46:0=RT , k7(T)=1013:7e-42:1=RT , k8(T)=1013:6e-51:8=RT and k9(T)=1015:6e-54:3=RT s-1, respectively. The calculated overall rate constants is 6.9￡10-4 at 543 K, which is in good agreement with the experimental data. Based on the analysis of the rate constants, the dominant pathway is the isomerization reaction to form CH3NN(OH)O at low temperatures, while the NN bond fission and the isomerization reaction to produce CH3NHONO are expected to be competitive with the isomerization reaction to form CH3NN(OH)O at high temperatures.     

甲烷与HO2反应的微观动力学研究

应用从头算方法和变分过渡态理论,在B3LYP/6-311+G^**方法下和300～2000K温度范围内研究甲烷与HO₂反应的微观动力学特性,得到由过渡态向反应物方向、向产物方向的能垒分别是11.83和102.90kJ/mol,理论计算正向反应速率常数与实验值之比为1.08～2.85,用此方法还可以预测没有实验数据的温度点反应的速率常数.     

Elimination of non-uniform, extra-device flow effects in membrane adsorbers

Commercial use of membrane adsorbers in the biotechnology industry is increasing. Here the system time lag created by membrane adsorber peripherals and the membrane adsorber flow distribution headers has been modeled using an anion exchange membrane and bovine serum albumin (BSA). The system time lag was modeled as a zero order and first order time lag. The zero and first order time lags have been removed from the breakthrough curve. The method used does not involve fitting a mathematical expression to the breakthrough curve. Further no assumptions are made regarding the shape of the breakthrough curve in the absence of the time lag. The method has been used to calculate the Langmuir isotherm parameters.The membrane capacity was found to be twice as large as the capacity determined after removal of the time lag. The Langmuir constant was five times as large for the system without accounting for the time lag. Errors in fitting isotherm parameters can significantly impact frontal analysis and membrane adsorber scale-up. The Langmuir isotherm calculated under dynamic conditions with the system time lag removed, was in agreement with the static adsorption isotherm.     

Global smoothness and uniform convergence of smooth Gauss–Weierstrass singular operators

In this article we continue with the study of smooth Gauss–Weierstrass singular integral operators over the real line regarding their simultaneous global smoothness preservation property with respect to the L_p norm, 1≤p≤∞, by involving higher order moduli of smoothness. Also we study their simultaneous approximation to the unit operator with rates involving the modulus of continuity with respect to the uniform norm. The produced Jackson type inequalities are almost sharp containing elegant constants, and they reflect the high order of differentiability of the engaged function.     

A note on wavelet density deconvolution for weakly dependent data

In this paper we investigate the performance of a linear wavelet-type deconvolution estimator for weakly dependent data. We show that the rates of convergence which are optimal in the case of i.i.d. data are also (almost) attained for strongly mixing observations, provided the mixing coefficients decay fast enough. The results are applied to a discretely observed continuous-time stochastic volatility model.     

Brownian运动连续模的拟必然收敛速率

在该文中, 作者得到了Brownian运动连续模在C_{r, p} - 容度意义下的泛函极限的收敛速率.     

A limit to alternate column recycle chromatography

Summary It was found experimentally that the potential for routine, rapid high-efficiency separations by alternate column, recycle, reversed-phase chromatography is limited by the increase of capacity factors with pressure.     

The rate of convergence for the cyclic projections algorithm III: Regularity of convex sets

The cyclic projections algorithm is an important method for determining a point in the intersection of a finite number of closed convex sets in a Hilbert space. That is, for determining a solution to the “convex feasibility” problem. This is the third paper in a series on a study of the rate of convergence for the cyclic projections algorithm. In the first of these papers, we showed that the rate could be described in terms of the “angles” between the convex sets involved. In the second, we showed that these angles often had a more tractable formulation in terms of the “norm” of the product of the (nonlinear) metric projections onto related convex sets.In this paper, we show that the rate of convergence of the cyclic projections algorithm is also intimately related to the “linear regularity property” of Bauschke and Borwein, the “normal property” of Jameson (as well as Bakan, Deutsch, and Li’s generalization of Jameson’s normal property), the “strong conical hull intersection property” of Deutsch, Li, and Ward, and the rate of convergence of iterated parallel projections. Such properties have already been shown to be important in various other contexts as well.     

Urban rapid transit network capacity expansion

This paper examines a multi-period capacity expansion problem for rapid transit network design. The capacity expansion is realized through the location of train alignments and stations in an urban traffic context by selecting the time periods. The model maximizes the public transportation demand using a limited budget and designing lines for each period. The location problem incorporates the user decisions about mode and route. The network capacity expansion is a long-term planning problem because the network is built over several periods, in which the data (demand, resource price, etc.) are changing like the real problem changes. This complex problem cannot be solved by branch and bound, and for this reason, a heuristic approach has been defined in order to solve it. Both methods have been experimented in test networks.     

横向数据中累加死亡率的估计-附脑血管病实例

本文用现时寿命表中计算平均寿命的基本假定,讨论估计横向数据的累加死亡率问题.本公式也适用于累加发病率及任何非医学领域中某种指标的累加发生率等问题.文中使用了一个脑血管病实例.