Direct dynamics study on mechanism and kinetics of the biradical self‐reaction of HOO

A theoretical study of the mechanism and the kinetics for the hydrogen abstraction reaction of the biradical hydroperoxy radical has been presented at the CCSD(T)/6‐311++G(3d,2p)//CCSD/6‐31+G(d,p) level of theory. Our theoretical calculations suppose a stepwise mechanism involving the formation of a postreactant complex in the triplet and singlet entrance channels. Four transition states of the six‐membered chain complexes (³TS1 and ¹TS1) and six‐membered ring complexes (³TS2 and ¹TS2) are located at the high dual level CCSD(T)/6‐311++G(3d,2p)//CCSD/6‐31+G(d,p) method. The rate constants of Path 1 ～ Path 4 at the CCSD(T)/6‐311++G(3d,2p)//CCSD/6‐31+G (d,p) level are calculated by means of the conventional transition state theory (TST) and canonical variational TST without and with small‐curvature tunneling (SCT) correction within the temperature range of 200–2,500 K. The calculated results show that the triplet channel is the dominating reaction channel and Path 2 is found to be the most favorable pathway. The rate constants of Path 2 are in good agreement with the experimental values at the experimentally measured temperatures. Moreover, the variational effect is not obvious in the low temperature range but is not neglectable in the high temperature range. The SCT plays an important role particularly in the low temperature range. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

金催化CO氧化湿度增强效应的理论研究

实验发现纳米金催化的CO氧化有良好的湿度增强效应,但有关机制仍不清楚.我们应用密度泛函理论研究了湿度增强效应的微观机制,以Au4团簇为例,研究了金催化CO氧化的微观机理,考察了H2O在反应中的角色和作用.计算结果表明,H2O与Au4团簇一样,在反应中扮演催化剂的角色,参与反应的进行、改变反应历程、降低反应能垒.催化循环包含4个基元步骤：O2＋H2O→OOH＋OH,CO＋OOH→CO2＋OH,CO＋OH→COOH,和COOH＋OH→CO2＋H2O,其中自由基OOH和OH的形成是催化循环的速控步骤,其能垒为100.31kJ/mol,明显低于非水参与反应的能垒（161.41kJ/mol）.目前的结果合理地解释了实验观测的CO催化氧化的湿度增强效应,给出了其微观反应机制.     

Kronecker product and a new matrix form of Lagrangian equations with multipliers for constrained multibody systems

The automatic derivation of motion equations is an important problem of multibody system dynamics. Firstly, an overview of the matrix calculus related to Kronecker product of two matrices is presented. A new matrix form of Lagrangian equations with multipliers for constrained multibody systems is then developed to demonstrate the usefulness of Kronecker product of two matrices in the study of dynamics of multibody systems. Finally, the equations of motion of mechanisms are derived using the proposed matrix form of Lagrangian equations as application examples.     

汶川震区文家沟泥石流成灾机理与特征

文家沟位于绵竹市清平乡,属于 5 ·12 汶川Ms8.0级地震极重灾区。地震发生后的3个汛期内,文家沟曾先后发生5次典型泥石流灾害,其中以2010年8月13日泥石流灾害最为严重,规模与灾情巨大,社会影响深远。在对文家沟泥石流跟踪调查的基础上,探讨了泥石流的成灾机理和特征。研究表明:(1)文家沟泥石流是地震和强降雨共同作用的结果,其成因可归纳为震因与物源以及雨因与水源两个方面,在整个泥石流形成和发生的过程中,呈现出洪流-侵蚀下切-崩滑-席卷-进一步侵蚀下切-进一步崩滑-增大泥石流规模—……的"滚雪球式"循环过程; (2)泥石流发生所需的雨量、雨强条件和水动力条件都显著降低,泥石流规模和雨量之间呈现出明显幂函数关系; (3)发生过程呈现出持续时间长、运动距离远的特征; (4)成灾过程呈现出明显的链式效应,危害形式多样; (5)泥石流频率呈现出高发性,规模呈现出放大性。最后提出了文家沟泥石流研究与防治的建议。     

铝板带冷轧过程中磨损影响因素 及磨损作用机制研究

轧后铝材表面磨损量是影响铝材轧制过程的重要因素,脱落的铝粉恶化产品表面质量、影响轧制效率。本文选用不同的添加剂配制轧制油,对铝板材进行冷轧试验,重点研究添加剂种类、铝材原始表面质量、轧制压下率三方面对铝材表面磨损性能及磨损机制的影响。结果表明：双组分添加剂轧制油中油性剂在金属表面吸附成膜,犁削磨损现象较无润滑和纯基础油轧制有明显改善,轧后铝材表面磨损量小;轧件轧前表面粗糙度大,轧辊对轧件微凸体的碾压作用加剧,被碾压下来的大量铝粉成为轧辊和轧件外的“第三体”,造成磨粒磨损加剧;化学磨损和犁削磨损同时存在于轧制过程中,油膜厚度较大时,前者是主要磨损机制;反之,后者起主导作用。     

碳纤维增强纸基摩擦材料磨损机理研究

以碳纤维为主要增强纤维,采用湿法工艺制备出1种纸基摩擦材料.研究了不同制动次数条件下样品的摩擦磨损行为,通过分析不同制动次数后样品磨损表面的粗糙度特征、三维轮廓形貌、微观形貌和热失重过程,探讨了碳纤维增强纸基摩擦材料的磨损机理.结果表明：随着制动次数的增加,磨损表面粗糙度大幅度降低,材料磨损过程经历了从＂跑合磨损＂到＂稳定磨损＂的转变;材料在磨损过程中微凸体逐渐被磨平,孔隙逐渐被填充,表现出疲劳磨损的特征;磨损后样品表层的热重曲线在320～450℃之间出现了新的剧烈失重峰,表明产生了热磨损;但是磨粒磨损的特征并不明显.     

接触表面不平度对摩擦尖叫噪声的影响

针对摩擦尖叫的间歇性特点,建立了考虑摩擦接触表面不平度的3自由度摩擦自激振动机理模型.应用数值方法分析了接触表面不平度倾角对系统稳定性及瞬态动力学特性的影响,并进行了基于销-盘装置的摩擦尖叫噪声试验研究.结果表明:系统的稳定性主要取决于系统自身的耦合特性,但也与摩擦特性和接触表面不平度倾角的综合作用有关.当接触表面不平度倾角增大时,系统趋向不稳定,会激发尖叫噪声.     

Existence results for functional first‐order coupled systems and applications

This paper is concerned with the existence of solutions of the first‐order fully coupled system with coupled functional boundary conditions. These functional boundary conditions generalize the usual boundary assumptions and may be applied to most of the classical cases. The arguments used are based on the Arzela‐Ascoli theorem and Schauder's fixed‐point theorem. An application to a mathematical model of the thyroid‐pituitary interaction and their homeostatic mechanism is included.     

基于SD-GM理论的城市交通拥堵收费模型研究

随着中国城市化建设步伐的不断加快,交通拥堵在不断地加剧。同时,因机动车污染物的排放,每年将产生大量的NO_x,从而又会引起严重的大气污染(如“雾霾”污染)。针对这些问题,本文从环境和社会的角度出发,采用系统动力学与灰色系统相结合的方法(SD-GM),构建了城市交通拥堵收费模型,并对模型中主要变量进行动态仿真和决策分析,以此来寻找缓解交通拥堵和减少机动车尾气排放的可行策略。通过现实性测试和敏感性测试,得到拥堵收费的范围不超过100元/天*辆。通过进一步的仿真和结果分析可得到以下结论:(1)在区间[25,40] 内,随着拥堵收费的提高,NO_x存量,机动车出行吸引度和交通拥堵程度都呈下降趋势,而车均道路面积呈上升趋势。(2)但并非拥堵收费越高越好, 超过40 元/天*辆,会产生相反的效果。最后,通过比较分析,得到NO_x存量,机动车出行量,机动车出行吸引度和交通拥堵程度分别下降了约33.76%,39.64%,43.26%,82.25%,而车均道路面积提高了大约65.68%,进而验证了模型的有效性和实用性。