Hamilton–Jacobi equation,reaction action surface and the emergence of the force concept in chemical reaction dynamics

A combination of Hamilton–Jacobi equation and fast marching algorithm can be used to study reaction dynamics by converting the potential energy surface to a reaction action surface. The reaction action surface has been found to be an important tool in theoretical chemistry, allowing us to provide a different force-based perspective of chemical reactions. Several properties such as reaction force, reaction force surface, reaction path force and reaction path force constant have been defined and calculated by using the reaction action surface. This paper investigates these newly defined properties in order to understand the role they play in chemical reaction with reference to a model 4-well potential energy surface.     

弹性地基上转动FGM梁自由振动的DTM分析

基于Euler-Bernoulli梁理论,利用广义Hamilton原理推导得到弹性地基上转动功能梯度材料(FGM)梁横向自由振动的运动控制微分方程并进行无量纲化,采用微分变换法(DTM)对无量纲控制微分方程及其边界条件进行变换,计算了弹性地基上转动FGM梁在夹紧-夹紧、夹紧-简支和夹紧-自由三种边界条件下横向自由振动的无量纲固有频率,再将控制微分方程退化到无转动和地基时的FGM梁,计算其不同梯度指数时第一阶无量纲固有频率值,并和已有文献的FEM和Lagrange乘子法计算结果进行比较,数值完全吻合。计算结果表明,三种边界条件下FGM梁的无量纲固有频率随无量纲转速和无量纲弹性地基模量的增大而增大;在一定无量纲转速和无量纲弹性地基模量下,FGM梁的无量纲固有频率随着FGM梯度指数的增大而减小;但在夹紧-简支和夹紧-自由边界条件下,一阶无量纲固有频率几乎不变。     

Computing reaction paths of a bifurcation reaction: an action wave-front-based perspective

Application of Hamilton–Jacobi (HJ) equation to reaction systems which involve energy barrier(s) leading to the product is relatively new. Such problems are described by a new class of HJ equation, called the generalised HJ equation. This new HJ equation renders an anisotropic propagation for the wave front. In this paper, we describe the adaptation of the fast marching method (FMM) and the generalised HJ equation to understand a new class of reaction process where the energy barrier does not lead to the product; instead, a new class of states are detected along the reaction path of such reactions. These states are valley-ridge inflection point, branching point and potential energy ridge. Such reactions are characterised as bifurcation reactions. We have identified a new classical wave front, called the reaction action front (RAF) which distinctly separates the reaction system into a reactant zone and a product zone connected by a third zone, called ‘neck’. The RAF is an important tool to understand the bifurcation reaction and the associated reaction paths. We have also introduced a convenient way to compute the reaction path force (RPF) using the FMM. The RPF for a bifurcation reaction significantly differs from the reactions with energy barrier, and so, the RPF provides vital information about the occurrence of branching of a path. The method has been tested for the isomerisation reaction of methoxy radical (H₃C) to hydroxymethylene radical (H₂?OH).     

Love–Bishop rod solution based on strain gradient elasticity theory

In the present work, the propagation of longitudinal stress waves is investigated with a strain gradient elasticity theory given by Lam et al. In principle, the analysis of wave motion is based on the Love rod model including the lateral deformation effects, but in the same time is also taken into account the shear strain effects with Bishop?s correction. By applying Hamilton?s principle, a general explicit strain gradient elasticity solution is developed for the longitudinal stress waves, and it is compared with the special solutions based on the modified couple stress and classical theories. This work gives useful information with regard to the meaning of the three scale parameters in the strain gradient elasticity theory used here.     

图的度和与扩路

本文讨论了两顶点的度和与路可扩之间的关系,得到了如下结果:设G是n阶图,如果G中任意一对不相邻的顶点u,v满足d(u)+d(v)≥n+n/k(2≤k≤n-2),则G中任意一个满足k+1≤|P|相似文献   

托卡马克中带电粒子的直接损失问题研究

首次发现了托卡马克中存在迥异于通行粒子和香蕉粒子的第三种粒子, 这种粒子会由于漂移运动而摆脱磁场的约束. 研究了该类粒子在其速度空间上的类磁镜损失锥, 给出了这一损失锥的数学表达式, 分析了存在这一类粒子的物理成因, 模拟与数学分析的结果基本一致. 研究还发现, 回旋半径在二阶条件下带电粒子的轨道损失高于零阶情况, 且与装置参数密切相关.     

Combining Modular Ligation and Supramolecular Self‐Assembly for the Construction of Star‐Shaped Macromolecules

A well‐defined random copolymer of styrene (S) and chloromethylstyrene (CMS) featuring lateral chlorine moieties with an alkyne terminal group is prepared (P(S‐co‐CMS), = 5500 Da, PDI = 1.13). The chloromethyl groups are converted into Hamilton wedge (HW) entities (P(S‐co‐HWS), = 6200 Da, PDI = 1.13). The P(S‐co‐HWS) polymer is subsequently ligated with tetrakis(4‐azidophenyl)methane to give HW‐functional star‐shaped macromolecules (P(S‐co‐HWS))₄, = 25 100 Da, PDI = 1.08). Supramolecular star‐shaped copolymers are then prepared via self‐assembly between the HW‐functionalized four‐arm star‐shaped macromolecules ( P(S‐co‐HW )) ₄ and cyanuric acid (CA) end‐functionalized PS (PS–CA, = 3700 Da, PDI = 1.04), CA end‐functionalized poly(methyl methacrylate) (PMMA–CA, = 8500 Da, PDI = 1.13) and CA end‐functionalized polyethylene glycol (PEG–CA, = 1700 Da, PDI = 1.05). The self‐assembly is monitored by ¹H NMR spectroscopy and light scattering analyses.     

Fractional differential equations of motion in terms of combined Riemann—Liouville derivatives

In this paper,we focus on studying the fractional variational principle and the differential equations of motion for a fractional mechanical system.A combined Riemann-Liouville fractional derivative operator is defined,and a fractional Hamilton principle under this definition is established.The fractional Lagrange equations and the fractional Hamilton canonical equations are derived from the fractional Hamilton principle.A number of special cases are given,showing the universality of our conclusions.At the end of the paper,an example is given to illustrate the application of the results.     

奇异Hamilton系统矩阵的精细积分法

常规位移有限元的结构振动方程是n个二阶常微分方程组.采用一般交分原理推导,将结构振动问题引入Hamiltoil体系,将得到2n个一阶常微分方程组.精细积分法宜于处理一阶方程,应用于线性定常结构动力问题求解,可以得到在数值上逼近精确解的结果.对于非齐次动力方程,当结构具有刚体位移时,系统矩阵将出现奇异.本文借鉴全元选大元高斯-约当法求解线性方程组的经验,提出全元选大元法求奇异矩阵零本征解的方法,该方法可以简便快速地寻求奇异矩阵零本征值对应的子空间.利用Hamiltoil体系已有研究成果及Hamilton系统的共轭辛正交归一关系,迅速将零本征值对应的子空间分离出来,通过投影排除奇异部分,然后用精细积分法求得问题的解.数值算例表明,该方法对Hamilton系统奇异问题,处理方便,计算量小,易于实现,同时保持了精细算法的优点.     

Higher-Order Lagrangian Equations of Higher-Order Motive Mechanical System

In this paper, if the condition of variation δt=0 is satisfied, the higher-order Lagrangian equations and higher-order Hamilton's equations, which show the consistency with the results of traditional analytical mechanics, are obtained from the higher-order Lagrangian equations and higher-order Hamilton's equations. The results can enrich the theory of analytical mechanics.