Analytical solutions to rate equations including losses describing threshold pumped fiber lasers

An exact analytical expression to the threshold pump power has been deduced for rate equations including loss coefficients applicable to fiber lasers doped with quasi two-energy-level ions. Following the derivation of a closed-form expression for the variation of the pump power along the fiber, together with analytical solutions to the position dependent atom population density and laser power in terms of the pump power, we have analytically and fully solved rate equations describing threshold pumped fiber lasers. A comparison has also been made between the exact analytical result with the previous reported results, which indicates that various approximation have underestimated the threshold pump powers.     

臭氧与二乙胺和三乙胺气相反应的速率常数

利用自制的烟雾箱系统研究了臭氧与二乙胺和三乙胺的气相反应动力学. 实验过程中保证二乙胺和三乙胺浓度远远大于臭氧浓度, 使得实验在准一级条件下进行. 加入环己烷以消除实验过程中可能产生的OH自由基对反应的影响. 在(298±1) K和1.01×105 Pa条件下, 测得臭氧与二乙胺和三乙胺反应的绝对速率常数值分别为(1.33±0.15)×10^-17和(8.20±1.01)×10^-17 cm³·molecule^-1·s^-1. 与文献中已有的其它胺类的臭氧反应数据比较后发现, 臭氧与胺的反应可以用亲电反应机制来解释. 另外, 通过对比发现, 臭氧与三取代的烷基胺类的反应速率要远远大于其与二取代的烷基胺类的反应速率. 这在一定程度上可有助于解释外场观测到的气溶胶相中二烷基胺盐较多的事实. 利用测得的速率常数和大气中臭氧浓度, 还估算了二乙胺和三乙胺与臭氧反应的大气寿命. 结果显示, 与臭氧的反应是二乙胺和三乙胺在大气中的一种重要的消除途径, 尤其是在污染严重地区.     

Theoretical Studies on the Kinetics and Mechanisms of Reactions for Methyl Vinyl Ether and Ozone

The interconversion between the two distinct isomers of methyl vinyl ether (MVE), the formation of the primary ozonides from O3-initated reactions of MVE, the transformation between the primary ozonides, and the subsequent fragmentation were studied using quantum chemical methods at the BHandHLYP/6-311++G(d,p) level of theory for optimized geometries and frequency calculations and at the QCISD/6-31G(d,p) level for the single point energy calculations. The rate coe±cients were calculated for the temper-ature range 280-440 K by using the canonical transition state theory (TST). For ozone addition to MVE, there are two different possibilities discussed on the basis of two different possible orientations for ozone attack. The results of the theoretical study indicate that although the synperiplanar-MVE is 7.11 kJ/mol more stable than the antiperiplanar-MVE, the antiperiplanar-MVE plays a more important role in formation of the primary ozonides because the primary ozonides formed from the ozone addition antiperiplanar-MVE are more stable and the energy barriers corresponding to transition states are lower. The interconversion between the primary ozonides formed from the ozone addition to antiperiplanar-MVE is the most accessible compared with the transformations between other primary ozonides. The cleavage of the primary ozonides mainly leads to the formation of the CH2OO, which is in agreement with the experimental estimates. The calculated overall rate constant for the ozone-initiated reactions is 4.8×10-17cm3/(moleculec∙s) at 298.15 K, which agrees with the experimental value for ethyl vinyl ether     

偏氯乙烯悬浮聚合反应速率模型

通过实验研究了偏氯乙烯悬浮聚合反应动力学,比较了偏氯乙烯与氯乙烯聚合动力学行为的异同.在假定偏氯乙烯聚合反应发生在单体相和液固界面两个区域的基础上,提出了偏氯乙烯沉淀聚合反应速率模型.模型预测的转化率值几乎在全转化率范围内都与本文的偏氯乙烯悬浮聚合实验结果一致.     

硝基胍H迁移异构化反应动力学的从头计算研究

Theoretical studies on the α- and β-forms nitroguanidine were carried out using ab initio theoretical methods, at the MP2/6-31G(d,p) level. The predicted geometrical parameters were in good agreement with the available theoretical values, which calculated by other author. The three C-N bond lengths in α-form nitroguanidine were different, the longest bond length was 1.430 A, the shortest was 1.283 A. But they were almost similar in β-form, the longest was 1.375 A, the shortest was 1.322 A. Therefore there were conjugative effects in β-form but not in α-form. The calculated results also show that the β-form is stable with respect to the α-form from energetically, lower 28.16 kJ/mol corrected with zero point vibrational energy. The transition-state for the unimolecular isomerization was conformed by the IRC calculation. The calculated energy barrier for the direct intramolecular hydrogen atom transfer isomerization process was 132.95 kJ/mol. The isomerization reaction, exothermal reaction, is a typical intramolecular hydrogen atom synfacial transfer reaction. Rate constants of the isomerization reaction were evaluated within the temperature range of 200-1773 K by the classical transition state theory. The rate constant was 1.99×10-11 s-1 and the equilibrium constant was 1.00×105 at 298 K. With the temperature increasing, the equilibrium value decayed and the reaction process was more difficult.     

Studies on Rate Enhancement of Polymerization in NMRP

IntroductionNitroxide-mediated polymerization is the best ex-ample of stable free-radical polymerization(SFRP),which was first proposed by Rizzardoet al.[1]and waslater developed by Georgeset al.[2,3]and Hawker[4].In the presence of a nitroxide such as2,2,6,6-tetra-methylpiperidine-oxyl(TEMPO),the free radical poly-merization of styrene(St)proceeds with a polydispersitybelow1.3.Unfortunately,up to now,the long reactiontime and the high price of SFRP are the main draw-backs of this react…     

Rate effects on toughness in elastic nonlinear viscous solids

A micromechanics-based constitutive relation for void growth in a nonlinear viscous solid is proposed to study rate effects on fracture toughness. This relation is incorporated into a microporous strip of cell elements embedded in a computational model for crack growth. The microporous strip is surrounded by an elastic nonlinear viscous solid referred to as the background material. Under steady-state crack growth, two dissipative processes contribute to the macroscopic fracture toughness—the work of separation in the strip of cell elements and energy dissipation by inelastic deformation in the background material. As the crack velocity increases, voids grow in the strain-rate strengthened microporous strip, thereby elevating the work of separation. In contrast, the energy dissipation in the background material decreases as the crack velocity increases. In the regime where the work of separation dominates energy dissipation, toughness increases with crack velocity. In the regime where energy dissipation is dominant, toughness decreases with crack velocity. Computational simulations show that the two regimes can exist in certain range of crack velocities for a given material. The existence of these regimes is greatly influenced by the rate dependence of the void growth mechanism (and the initial void size) as well as that of the bulk material. This competition between the two dissipative processes produces a U-shaped toughness-crack velocity curve. Our computational simulations predict trends that agree with fracture toughness vs. crack velocity data reported in several experimental studies for glassy polymers and rubber-modified epoxies.     

N指标d维广义Wiener过程极集的性质

研究了Ｎ指标ｄ维广义Ｗｉｅｎｅｒ过程极集的性质,得到了其极性的必要条件．     

Cumulative prospect theory and imprecise risk

Tversky and Kahneman have worked out an appealing model of decision making under uncertainty, involving rank- and sign-dependent utilities. This model, cumulative prospect theory (CPT), as well as related models proposed by other authors, has received wide acclaim. Available information and psychological attitude facing ambiguity jointly determine the subjective likelihood values the decision maker attributes to events, expressed by either one of two capacities depending on the prospect of either gains or losses; unfortunately, neither interpretation of these capacities nor prevision of their links are straightforward. An insight into these issues is given by studying consistency of CPT with certain generalized expected utility models, when faced with objective data described by lower–upper probability intervals. Means of testing the existence of subjectively lower–upper probabilized events are obtained, as well as means of evaluating ambiguity aversion.     

丙酮酸和苯甲酰甲酸热分解反应的速率常数

用从头算方法在6-31G的水平上研究了丙酮酸和苯甲酰甲酸热分解反应的机理．反应过程中各驻点都进行MP2相关能校准．计算结果表明：这两个反应都是羟基氢经历五元环过渡态迁移到α-羰基氧上形成氢键中间体;然后氢键中间体直接分解成异构体和二氧化碳;最后异构体经历三元环过渡态异构化成相应的醛．其中氢迁是决速步骤．在MP2／6-31G／／HF／6-31G基础上,对应于这两个反应速控步骤的活化位垒分别是186．0kJ·mol-1和169．3kJ·mol-1．在传统过渡态理论的基础上,计算了这两个反应在一定温度范围内热速率常数,理论的计算结果与实验值有很好的吻合．