叔丁氧基自由基引发氢迁移过程的理论研究

采用多种密度泛函理论方法(如CAM-B3LYP, M062x和wB97x方法), 并辅以极化连续介质模型对叔丁氧基自由基(^tBuO·)与一系列胺类、 烷烃、 醇类和醚类反应物之间氢迁移反应的反应机理进行研究. 计算结果表明, 这类氢迁移反应主要受熵的控制. 通过对液相平动熵和气相平动熵得到的活化自由能数据进行对比, 可以看出, 使用气相平动熵得出的活化自由能明显偏高于实验测量值, 而以液相平动熵计算的反应活化自由能垒与实际结果相近, 3种方法对胺类和烷烃类反应物体系得出的结果更可靠, 对醇类和醚类反应物体系自由能垒则略低.     

On a variant of the Maxwell and Oldroyd-B models within the context of a thermodynamic basis

In this paper we develop models within a thermodynamic standpoint that are very similar in form to the classical Maxwell and Oldroyd-B models but differ from them in one important aspect, the manner in which they unload instantaneously from the deformed configuration. As long as the response is not instantaneous, the models that are derived cannot be differentiated from the Maxwell and Oldroyd-B models, respectively. The models can be viewed within the context of materials whose natural configuration evolves, the evolution being determined by the maximization of the rate of entropy production of the material. However, the underpinnings to develop the model are quite different from an earlier development by Rajagopal and Srinivasa [8] in that while the total response of the viscoelastic fluid satisfies the constraint of an incompressible material, the energy storage mechanism associated with the elastic response is allowed to be that for a compressible elastic solid and the dissipative mechanism associated with the viscous response allowed to be that for a compressible fluid, the total deformation however being isochoric. The analysis calls for a careful evaluation of firmly held customs in viscoelasticity wherein it is assumed that it is possible to subject a material to a purely instantaneous elastic response without any dissipation whatsoever. Finally, while the model developed by Rajagopal and Srinivasa [8] arises from the linearization of the non-linear elastic response that they chose and leads to a model wherein the instantaneous elastic response is isochoric, here we develop the model within the context of a different non-linear elastic response that need not be linearized but the instantaneous elastic response not necessarily being isochoric.     

Auq+(q=53-47)激光等离子体的辐射复合速率系数

辐射复合过程在超组态碰撞辐射(SCROLL)模型中真实模拟非局域热动力学平衡(non-LTE)高Z材料Au激光等离子体M带谱5f-3d跃迁中各种复杂离子的电离态特性是一个主要过程.基于准相对论多组态Hartree-Fock理论和扭曲波近似,采用组态平均的方法,从头计算了金M带类铁金离子-类锗金离子的辐射复合速率系数,计算过程中包含了大量的单激发和双激发态,结果表明高Z元素由于自电离能级的广泛分布和复杂的级联效应,致使高Z元素的辐射复合系数不同于低Z元素的,其计算结果可用来模拟Au的激光等离子体M带5f-3d跃迁的平均电离度和电荷态分布及能级布居数.     

高功率光子晶体光纤放大器内超短脉冲的放大传输特性

由速率方程和功率传输方程得到信号脉冲平均功率和增益系数随脉冲传输距离的变化关系.利用Ginzburg-landau方程,在信号脉冲功率的不断增强和增益系数的不断变化的情况下,研究超短脉冲的传输演化特性,发现信号脉冲平均功率、能量和增益系数等参量受到色散和非线性效应的影响相对较小,而信号脉冲的峰值功率、时域和频域特性则易受到色散和非线性效应的影响.探讨了在非线性作用下,脉冲分裂和展宽等所导致的脉宽不稳定性对传输特性的影响,表明研究脉冲传输问题时,引入脉宽不稳定性有利于提高数值模拟准确度.     

Reactions of small negative ions with O2(a Δg) and O2(X Σg)

The rate constants and product ion branching ratios were measured for the reactions of various small negative ions with O₂(X ³Σ_g⁻) and O₂(a ¹Δ_g) in a selected ion flow tube (SIFT). Only NH₂⁻ and CH₃O⁻ were found to react with O₂(X) and both reactions were slow. CH₃O⁻ reacted by hydride transfer, both with and without electron detachment. NH₂⁻ formed both OH⁻, as observed previously, and O₂⁻, the latter via endothermic charge transfer. A temperature study revealed a negative temperature dependence for the former channel and Arrhenius behavior for the endothermic channel, resulting in an overall rate constant with a minimum at 500 K. SF₆⁻, SF₄⁻, SO₃⁻ and CO₃⁻ were found to react with O₂(a ¹Δ_g) with rate constants less than 10⁻¹¹ cm³ s⁻¹. NH₂⁻ reacted rapidly with O₂(a ¹Δ_g) by charge transfer. The reactions of HO₂⁻ and SO₂⁻ proceeded moderately with competition between Penning detachment and charge transfer. SO₂⁻ produced a SO₄⁻ cluster product in 2% of reactions and HO₂⁻ produced O₃⁻ in 13% of the reactions. CH₃O⁻ proceeded essentially at the collision rate by hydride transfer, again both with and without electron detachment. These results show that charge transfer to O₂(a ¹Δ_g) occurs readily if the there are no restrictions on the ion beyond the reaction thermodynamics. The SO₂⁻ and HO₂⁻ reactions with O₂(a) are the only known reactions involving Penning detachment besides the reaction with O₂⁻ studied previously [R.S. Berry, Phys. Chem. Chem. Phys., 7 (2005) 289–290].     

人民币汇率波动与我国房价关系的实证分析

分析了汇率影响房价的机制,利用人民币实际有效汇率、房地产价格指数和银行同业拆借利率共30组数据(2005,07～2007,12)建立了向量自回归模型(VAR),并使用协整、Granger因果检验,脉冲响应分析对人民币汇率波动与我国房地产价格之间的关系进行实证检验.研究结果表明,人民币实际有效汇率对房地产价格产生正向影响,人民币升值是引起房价上涨的格兰杰原因.在现阶段,控制因人民币升值而进入中国的境外资金过度流入房地产市场,有利于保持我国房地产价格稳定.     

基于R/S分析的专利申请量年增长率的相关性研究

Hurst指数是描述分数布朗运动的重要指标.利用R/S分析方法计算出我国专利申请量年增长率的Hurst指数稳定在0.62附近,分形维数稳定在1.38附近.表明我国专利申请量年增长率时间序列,服从分数布朗运动,专利申请量年增长率具有长期相关性.历史数据的影响力随时间间隔的长度增长而缩小,当间隔长度达到10年以上时,历史数据的影响力趋于稳定.     

Effect of added donor ligands on the selective oxygenation of organic sulfides by oxo(salen)chromium(V) complexes

Oxo(salen)chromium(V) complexes, [(salen)Cr^VO]⁺, oxidize organic sulfides selectively to sulfoxides in high yield. This oxygenation reaction is catalyzed by ligand oxides (LO's), pyridine N-oxide, 4-picoline N-oxide, 4-phenyl pyridine N-oxide and triphenylphosphine oxide. The rate is accelerated by 10-20 times with an increase in yield of sulfoxide in less reaction time. This catalytic activity is highly sensitive to the nature of the substituent in the phenyl ring of ArSMe and in the 3- and 5-position of the salen ligand. The reaction constant (ρ) value obtained with the ligand oxide catalyzed reaction is low compared to the value in the absence of LO. The strong binding and catalytic activity of ligand oxides on the oxo(salen)chromium(V) ion oxygenation is explained in terms of binding constants and a mechanism involving the electrophilic attack of [(salen)Cr^VO]⁺-LO adduct on the sulfur centre of phenyl methyl sulfide.     

Oxidation of polyethylene under irradiation at low temperature and low dose rate. Part II. Low temperature thermal oxidation

This paper deals with the kinetic modelling of unstabilised polyethylene thermal oxidation, particular attention being paid to the domain of low temperatures, typically below 80 °C. Experimental data show that the temperature dependence of the induction time t_i and the steady state rate of oxygen absorption r_S display a discontinuity at 80 °C. A model based on the hypothesis that this discontinuity concerns only the PO₂ bimolecular combination processes and is essentially explained by the competition between terminating and non-terminating PO₂ + PO₂ reactions, was proposed. With pertinent values of the Arrhenius parameters of the elementary reactions under consideration, the model fits well the experimental data (in the 40-200 °C temperature range) and is consistent with previously analysed results of radiochemical ageing. According to this model, 35-40% of the bimolecular PO₂ combinations would not be terminating at 45 °C and this proportion would increase with the temperature. Concerning terminations, the relative fraction of coupling processes, leading to peroxide bridges, would decrease relatively to the disproportionation processes when the temperature increases.     

Eigenfunction statistics on quantum graphs

We investigate the spatial statistics of the energy eigenfunctions on large quantum graphs. It has previously been conjectured that these should be described by a Gaussian Random Wave Model, by analogy with quantum chaotic systems, for which such a model was proposed by Berry in 1977. The autocorrelation functions we calculate for an individual quantum graph exhibit a universal component, which completely determines a Gaussian Random Wave Model, and a system-dependent deviation. This deviation depends on the graph only through its underlying classical dynamics. Classical criteria for quantum universality to be met asymptotically in the large graph limit (i.e. for the non-universal deviation to vanish) are then extracted. We use an exact field theoretic expression in terms of a variant of a supersymmetric σ model. A saddle-point analysis of this expression leads to the estimates. In particular, intensity correlations are used to discuss the possible equidistribution of the energy eigenfunctions in the large graph limit. When equidistribution is asymptotically realized, our theory predicts a rate of convergence that is a significant refinement of previous estimates. The universal and system-dependent components of intensity correlation functions are recovered by means of an exact trace formula which we analyse in the diagonal approximation, drawing in this way a parallel between the field theory and semiclassics. Our results provide the first instance where an asymptotic Gaussian Random Wave Model has been established microscopically for eigenfunctions in a system with no disorder.