Molecular Orbitals and Organic Chemical Reactions, Student Edition

Molecular Orbitals and Organic Chemical Reactions, Student Edition pdf epub mobi txt 电子书 下载 2026

出版者:Wiley
作者:Ian Fleming
出品人:
页数:376 pages
译者:
出版时间:2010-1-26
价格:$57.95
装帧:Paperback
isbn号码:9780470746592
丛书系列:
图书标签:
  • 化学
  • Molecular Orbitals
  • Organic Chemistry
  • Chemical Reactions
  • Organic Reactions
  • Frontier Molecular Orbital Theory
  • Woodward-Hoffmann Rules
  • Pericyclic Reactions
  • Stereochemistry
  • Spectroscopy
  • Reaction Mechanisms
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具体描述

Product Description

Molecular orbital theory is used by chemists to describe the arrangement of electrons in chemical structures. It is also a theory capable of giving some insight into the forces involved in the making and breaking of chemical bonds—the chemical reactions that are often the focus of an organic chemist’s interest. Organic chemists with a serious interest in understanding and explaining their work usually express their ideas in molecular orbital terms, so much so that it is now an essential component of every organic chemist’s skills to have some acquaintance with molecular orbital theory.

Molecular Orbitals and Organic Chemical Reactions is both a simplified account of molecular orbital theory and a review of its applications in organic chemistry; it provides a basic introduction to the subject and a wealth of illustrative examples. In this book molecular orbital theory is presented in a much simplified, and entirely non-mathematical language, accessible to every organic chemist, whether student or research worker, whether mathematically competent or not. Topics covered include:

* Molecular Orbital Theory

* Molecular Orbitals and the Structures of Organic Molecules

* Chemical Reactions — How Far and How Fast

* Ionic Reactions — Reactivity

* Ionic Reactions — Stereochemistry

* Pericyclic Reactions

* Radical Reactions

* Photochemical Reactions

Molecular Orbitals and Organic Chemical Reactions: Student Edition is an invaluable first textbook on this important subject for students of organic, physical organic and computational chemistry.

From the Back Cover

Molecular orbital theory is used by chemists to describe the arrangement of electrons in chemical structures. It is also a theory capable of giving some insight into the forces involved in the making and breaking of chemical bonds—the chemical reactions that are often the focus of an organic chemist’s interest. Organic chemists with a serious interest in understanding and explaining their work usually express their ideas in molecular orbital terms, so much so that it is now an essential component of every organic chemist’s skills to have some acquaintance with molecular orbital theory.

Molecular Orbitals and Organic Chemical Reactions is both a simplified account of molecular orbital theory and a review of its applications in organic chemistry; it provides a basic introduction to the subject and a wealth of illustrative examples. In this book molecular orbital theory is presented in a much simplified, and entirely non-mathematical language, accessible to every organic chemist, whether student or research worker, whether mathematically competent or not. Topics covered include:

* Molecular Orbital Theory

* Molecular Orbitals and the Structures of Organic Molecules

* Chemical Reactions — How Far and How Fast

* Ionic Reactions — Reactivity

* Ionic Reactions — Stereochemistry

* Pericyclic Reactions

* Radical Reactions

* Photochemical Reactions

This expanded Reference Edition of Molecular Orbitals and Organic Chemical Reactions takes the content and the same non-mathematical approach of the Student Edition, and adds extensive extra coverage, detail and over 1800 references. The additional material adds a deeper understanding of the models used, and includes a broader range of applications and case studies. Providing a complete reference for an advanced audience, this edition will find a place on the bookshelves of researchers and advanced students of organic, physical organic and computational chemistry --This text refers to the Hardcover edition.

理论化学与结构分析导论 本书旨在为初、中级化学学习者提供一套全面、深入的无机、有机及物理化学基础知识体系。重点关注现代化学研究中不可或缺的理论模型、计算方法以及它们如何精确地描述分子结构、键合特性和宏观反应机理。 --- 第一部分:量子力学基础与原子结构 本部分内容奠定了理解所有化学现象的理论基石——量子力学的基本原理。内容严格遵循从基础公设到实际应用的逻辑顺序,确保读者能够逐步构建起清晰的理论图像。 第一章:量子力学的公设与薛定谔方程 1.1 物质波的德布罗意假设: 探讨粒子-波二象性,引入动量与波长的关系,为处理电子行为做铺垫。 1.2 薛定谔方程的建立: 详细介绍定态和含时薛定谔方程的数学形式,阐述哈密顿算符在分子系统中的具体表达,包括动能和势能项的精确描述。 1.3 波函数的物理意义: 深入解析波函数 $Psi$ 的概率解释(玻恩诠释),讨论归一化条件、正交性和完备性,强调其在确定系统状态中的核心地位。 1.4 算符、本征值与平均值: 系统介绍线性算符的性质,解释测量操作对应于算符作用于波函数产生本征值,以及如何通过积分计算可观测量(如能量、角动量)的平均值。 第二章:单电子原子与角动量理论 2.1 氢原子的精确解: 详述三维球坐标系下的拉普拉斯算符转换,分离变量法求解径向方程和角向方程,导出主量子数 ($n$)、角量子数 ($l$) 和磁量子数 ($m_l$) 的物理意义和取值规则。 2.2 电子的轨道与自旋角动量: 引入轨道角动量算符 $mathbf{L}$ 及其算符代数,计算其本征值。随后,基于斯特恩-盖拉赫实验,引入电子自旋角动量 $mathbf{S}$ 和自旋量子数 ($m_s$),解释泡利不相容原理的起源。 2.3 多电子原子中的近似方法: 讨论处理复杂原子体系的挑战,详细介绍斯莱特有效核电荷模型 ($Z_{eff}$),解释屏蔽效应,并将其应用于解释元素周期律中的电离能和原子半径趋势。 第二部分:分子结构与化学键理论 本部分将理论物理概念应用于多原子体系,重点解析化学键的本质、分子轨道的构建方法,并结合群论工具预测分子几何和光谱特性。 第三章:分子轨道理论的构建(LCAO-MO) 3.1 线性组合原子轨道(LCAO)近似: 详细阐述将原子轨道线性组合构建分子轨道的理论依据,包括轨道对称性匹配的重要性。 3.2 针对双原子分子($A_2$)的轨道图: 分别推导和绘制同核双原子分子(如 $ ext{H}_2, ext{He}_2, ext{N}_2$)的 $sigma$ 和 $pi$ 轨道能量图,精确计算键级(Bond Order)并解释其与键稳定性的关系。 3.3 异核双原子分子与极性键: 讨论电负性差异对分子轨道能量和形状的影响,引入偶极矩的概念,解释离子性和共价性的连续性。 第四章:多原子分子轨道理论与分子几何 4.1 组成分子轨道的原子轨道选择: 讨论如何根据分子几何和轨道重叠积分(Overlap Integral)选择参与构建MO的原子轨道集合。 4.2 群论在分子对称性分析中的应用: 介绍点群、对称操作、特征标表。重点讲解如何使用特征标表来确定分子轨道的不可约表示(Irreducible Representations),这是判断轨道能否有效重叠的关键。 4.3 骨架结构的MO构建实例: 以 $ ext{H}_2 ext{O}$($C_{2v}$)和 $ ext{BF}_3$($D_{3h}$)为例,系统演示如何通过群论方法构建核心骨架的分子轨道,并识别最高占据分子轨道(HOMO)和最低未占据分子轨道(LUMO)。 第五章:价层电子对互斥理论(VSEPR)与杂化理论 5.1 VSEPR模型的应用范围与局限性: 阐述如何利用孤对电子和成键电子对的斥力来快速预测分子构象,并讨论其在处理过渡金属络合物时的局限。 5.2 经典杂化概念的深入理解: 详细分析 $ ext{sp}, ext{sp}^2, ext{sp}^3$ 杂化的几何构型,并扩展到 $ ext{sp}^3d$ 和 $ ext{sp}^3d^2$ 杂化在五配位和六配位体系中的表现。 5.3 晶体场理论(CFT)与配位场理论(LFT)基础: 简要介绍如何使用CFT解释过渡金属配合物的颜色和磁性,重点分析d轨道在不同几何配位场下的能级分裂情况(如八面体和四面体场)。 第三部分:化学反应的电子基础与动力学描述 本部分将理论工具应用于预测和理解化学转化的内在机制,特别是对于有机化学中至关重要的电子流和反应路径的分析。 第六章:电子流动的描述与反应活性 6.1 反应性指标: 引入HOMO-LUMO能量差和轨道系数的分析方法,解释轨道相互作用如何决定反应发生的难易程度和区域选择性。 6.2 局部反应活性分析: 运用电荷密度(如Mulliken电荷、NBO分析)和分子静电势(MEP)图,解释亲电取代和亲核加成反应的位点选择性。 6.3 芳香性与共轭体系: 基于Hückel分子轨道(HMO)理论,分析平面环状共轭体系的稳定性,推导 $4n+2$ 规则的理论基础,并计算共轭体系的离域化能。 第七章:化学反应性理论——过渡态与反应势能面 7.1 反应坐标与过渡态: 定义反应势能面(Potential Energy Surface, PES),明确势能面上的鞍点(Saddle Point)对应于过渡态(Transition State, TS)。 7.2 活化能与阿伦尼乌斯方程的微观解释: 从统计力学角度解释宏观动力学常数与微观能量壁垒(活化能 $E_a$)的联系,并引入碰撞理论的修正。 7.3 反应路径分析(IRC): 介绍如何通过反向积分(Intrinsic Reaction Coordinate, IRC)从过渡态追踪反应物和产物的结构,从而完整描绘反应机理。 --- 附录: 包含常用数学工具回顾(矩阵代数、微积分回顾)以及常用分子点群的特征标表。 本书特色: 本书避免了对具体有机反应机理的详尽罗列,而是专注于提供一个坚实的、可跨越学科界限的理论框架。每一个理论工具(如LCAO、群论、PES分析)都与具体的化学现象(如键合、分子形状、反应速率)紧密关联,为读者未来的高级计算化学或机理研究打下坚实基础。理论推导力求严谨,但最终解释均回归化学直观。

作者简介

Ian Fleming (1935 – present) is an English organic chemist, and an emeritus professor of the University of Cambridge. He was the first to determine the full structure of chlorophyll (in 1967) and was involved in the development of the synthesis of vitamin B12 by Robert Burns Woodward. He has made major contributions to the use of organosilicon compounds for stereospecific syntheses; reactions which have found application in the synthesis of natural compounds. He is also a prolific author, and has written a number of textbooks, encyclopedia chapters and influential review articles.

Life and research

Ian Fleming was born in Staffordshire and grew up in Stourbridge, Worcestershire. He received a B.A. in 1959 and a Ph.D. in 1962, both from Pembroke College, Cambridge. His post-doctoral studies were done at Harvard University with R.B. Woodward on the synthesis of vitamin B12. He has made advances in the topic of stereochemistry, developing new synthetic reactions. He has also pioneered the applications of organosilicon chemistry for organic synthesis, especially for the production of chiral molecules, and synthesized the highly stable 8-cycloheptatrienylheptafulvenyl carbocation.

Prof. Fleming has an extensive list of publications, including major contributions to the chemical encyclopedia "Comprehensive Organic Chemistry", and many influential review articles. He has also authored popular undergraduate textbooks on spectroscopic methods of structure determination, organic synthesis, and applications of frontier orbital theory to problems in organic chemistry.

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