1
课程详述
COURSE SPECIFICATION
以下课程信息可能根据实际授课需要或在课程检讨之后产生变动。如对课程有任何疑问,请联
系授课教师。
The course information as follows may be subject to change, either during the session because of unforeseen
circumstances, or following review of the course at the end of the session. Queries about the course should be
directed to the course instructor.
1.
课程名称 Course Title
物理化学 II Physical Chemistry II
2.
授课院系
Originating Department
化学系 Department of Chemistry
3.
课程编号
Course Code
CH302
4.
课程学分 Credit Value
4
5.
课程类别
Course Type
专业基础课 Major Foundational Courses
6.
授课学期
Semester
春季 Spring
7.
授课语言
Teaching Language
中英双语 English & Chinese
8.
他授课教师)
Instructor(s), Affiliation&
Contact
For team teaching, please list
all instructors
李炳瑞 教授,13919413455
Bingrui Li, Professor. Mobile: 13919413455
黄立民教授,(0755) 88018308
Prof. Limin Huang. Office: (0755) 88018308
9.
/
方式
Tutor/TA(s), Contact
待公布 To be announced
10.
选课人数限额(不填)
Maximum Enrolment
Optional
授课方式
Delivery Method
习题/辅导/讨论
Tutorials
实验/实习
Lab/Practical
其它(请具体注明)
OtherPlease specify
总学时
Total
11.
学时数
Credit Hours
64
2
12.
先修课程、其它学习要求
Pre-requisites or Other
Academic Requirements
物理化学 ICH301
13.
后续课程、其它学习规划
Courses for which this course
is a pre-requisite
14.
其它要求修读本课程的学系
Cross-listing Dept.
教学大纲及教学日历 SYLLABUS
15.
教学目标 Course Objectives
本课程的主要教学目标是:通过物理化学 II 的课堂讲授教学,使学生系统地掌握中级及高级物理化学的基本原理和学法,
来认识和研究物质内部本质原理,化学运动的普遍规律以及光谱的产生和应用,并培养学生运用物理化学的原理和方法来
分析和解决实际问题,训练学生建立广泛且深入的思维方式,一方面增强他们在今后从事化学教学和科研工作的实际能
力,另一方面帮助学生全面均衡地思考并解决与物理化学相关的实际问题。
The goal of Physical Chemistry II is to enable students to grasp the basic principles (the universal law of chemical
movement as well as spectrum production and the application) of intermediate level and the advanced Physical
Chemistry systematically, to help students establish a broad and deep thinking mode, and to train them to use the
principles and methods of physical chemistry to analyze and solve practical problems in future research work.
16.
预达学习成果 Learning Outcomes
通过学习物理化 II 课程,理解物质结构与其性质的关系,掌握研究物质结构的基本理论和方法,认识化学过程、机理
其控制因素。
*掌握量子力学基础知识,了解薛定谔方程在微观体系研究中的重要作用;
*掌握简单体系(尤其是一维和三维无限深势阱中粒子模型)薛定谔方程的求解;
*了解分子轨道理论要点,用于理解和说明一些分子的结构和性质;
*能够确定分子的点群,掌握对称性在化学中的初步应用技巧;
*理解晶体的点阵理论和 X 射线衍射原理,熟悉一些典型的晶体结构;
*了解转动、振动、电子光谱,磁共振谱和能谱的基本原理及其化学应用;
*了解分子内和分子间相互作用种类,偶极矩,极化等概念;
*了解分子在气相,液相中的相互作用;
* 理解化学反应的速率和机理问题。
Through the study of Physical Chemistry II, students should understand the basic principles, laws and methods that
govern the chemical behaviours of a chemical system from macroscopic to microscopic levels, which includes:
* Basic knowledge of quantum mechanics and understand the important role of Schrodinger's equation in the study of
microscopic systems;
* Solution of the Schrodinger equation of a simple system;
* Molecular orbital theory for describing the structure and property of molecules;
* Group theory of molecules and the symmetry in chemistry;
* Crystal theory and the principle of X-ray diffraction, some typical crystal structures;
* Basic principles of rotation, vibration, electron spectroscopy, magnetic resonance spectroscopy and energy spectrum
and their chemical applications;
* Concepts of intermolecular interactions, dipole moments, polarization, and etc.;
3
* Interaction of molecules in gas phase and liquid phase;
* Rate and mechanism of chemical reactions.
17.
课程内容及教学日历 (如授课语言以英文为主,则课程内容介绍可以用英文;如团队教学或模块教学,教学日历须注明
主讲人)
Course Contents (in Parts/Chapters/Sections/Weeks. Please notify name of instructor for course section(s), if
this is a team teaching or module course.)
物理化学 II 主要内容是结构化学,以及化学反应动力学。探讨和解决下列问题:量子力学基本原理及其化学应用,分
结构与其性能的关系;光谱的产生与应用;晶体结构几何理论与 X 射线衍射原理;化学反应的速率和机理等。具体有以下
内容:
Physical Chemistry II mainly discusses structural chemistry as well as reaction kinetics. It includes the basic principle of
quantum mechanics and its application in chemistry, the relationship between molecular structure and its properties, the
generation and application of spectra, the geometric theory of crystal structure and the principle of X-ray diffraction, the
rate and mechanism of chemical reactions, and etc. The detailed contents are as the following:
Lecture 1: The origins of quantum mechanics (2 units)
1. 量子力学基础(Introduction to quantum mechanics
1.1 量子力学的起源(The origins of quantum mechanics
1.1.1 黑体辐射与能量量子化(Black-body radiation and energy quantization
1.1.2 光电效应与光量子化(Photoelectric effect and photons
1.1.3 原子光谱与轨道角动量量子化(Atomic spectra and orbital angular momentum quantization
1.2 量子力学的建立(Establishment of quantum mechanics
1.2.1 实物粒子的波粒二象性(Wave-particle duality of physical particles
相关文段 1.1 电子显微镜(BOX 1.1: Electron microscopy
1.2.2 Schrödinger 方程(The Schrödinger equation
Lecture 2: Quantum mechanical principles (2 units)
1.2.3 波函数的 Born 解释(The Born Interpretation of the wave function
1.2.4 不确定原理(The uncertainty principle
1.2.5 量子力学公设(The postulates of quantum mechanics
(1) 波函数(Wavefunctions
(2) 算符(Operators
(3) 本征值与本征函数(Eigenvalues and eigenfunctions
(4) 态叠加原理与期望值(Superpositions and expectation values
(5) Pauli 原理(The Pauli principle
4
Lecture 3: A particle in a box (2 units)
1.3 阱中粒子的量子特征(Quantum characteristics of particle in wells
1.3.1 一维无限深势阱中的粒子(A particle in a box
(1) 合格解(Acceptable solutions
(2) 归一化(Normalization
(3) 解的性质(The properties of the solutions
(4) 正交性与 Dirac 括号(Orthogonality and the bracket notation
1.3.2 三维无限深势阱中的粒子(Motion in three-dimensions
(1) 变量分离(Separation of variables
(2) 简并性(Degeneracy
相关文段 1.2 量子点的发射光谱(BOX 1.2: The emission spectrum of quantum dots
1.4 隧道效应与扫描探针显微技术(Tunneling and scanning microscopy
Lecture 4: Atomic structure (2 units)
2. 原子结构(Atomic structure
2.1 单电子原子的结构(The structure of hydrogenic atoms
2.1.1 单电子原子 Schrödinger 方程(The Schrödinger equation for hydrogenic atoms
2.1.2 坐标变换与变量分离(Transformation of coordinates and separation of variables
2.1.3 方程的求解:原子轨道与能级(The solution of the equation: Atomic orbitals and their energies
(1) 能级(The energy levels
(2) 壳层与支壳层(Shells and subshells
(3) 原子轨道( Atomic orbitals
2.1.4 Virial 定理与零点能(The virial theorem and zero point energy
相关文段 2.1 Rydberg 原子(BOX 2.1 Rydberg atoms
2.2 原子轨道和电子云的图形表示(Graphics of atomic orbits and electron density
2.2.1 径向部分与角度部分的对画图(Painting of the radial and the angular wavefunctions
2.2.2 等值面图与界面图:函数参数化
The contour and the boundary surfaces: Parameterization for wavefunction
5
2.2.3 网格图:坐标参数化(The network graphics: Parameterization for coordinate
2.2.4 电子云黑点图(The black dot map of electron density
2.2.5 原子轨道的宇称(Parity of atomic orbitals
Lecture 5: The structures of many-electron atoms (2 units)
2.3 算符与可测物理量(Operators and physical quantities
2.3.1 角动量与量子数(The angular momentum and quantum numbers
2.3.2 角动量的空间量子化(Space quantization of angular momentum
2.4 多电子原子的结构(The structures of many-electron atoms
2.4.1 Schrödinger 方程(The Schrödinger equation
2.4.2 单电子近似与中心力场近似(Single electron approximation and central field approximation
2.4.3 自洽场方法(SCF)(Self-consistent field methodSCF
2.4.4 构造原理与电子组态(The building-up principle and the configurations
2.4.5 Slater 行列式(The Slater determinant
2.5 原子结构参数(Atomic structure parameters
2.5.1 电离能(Ionization energies
2.5.2 电子亲和势(Electron affinities
2.5.3 电负性(Electronegativity
2.5.4 化学硬度(Chemical hardness
Lecture 6: Term symbols (2 units)
2.6 原子光谱项(Term symbols
2.6.1 组态与状态(The configuration and the states
2.6.2 矢量耦合模型(Vector model
2.6.3 谱项与支项(Terms and levels
(1) 总轨道角动量(The total orbital angular momentum
(2) 自旋多重度(The multiplicity
(3) -轨耦合(Spin–orbit coupling
(4) 总角动量(The total angular momentum
6
2.6.4 Hund 规则(The Hund rules
2.6.5 跃迁选律(Spectroscopic transitions and selection rules
相关文段 2.2 亚稳态与激光(BOX 2.2 Metastable states and laser
2.6.6 Zeeman 效应(Zeeman effects
Lecture 7: Molecular orbital theory (2 units)
3. 分子结构与化学键理论(Molecular structures and theory of chemical bonds
3.1 Born-Oppenheimer 近似(The Born–Oppenheimer approximation
3.2 变分原理(The variation principle
3.3 分子轨道理论(Molecular orbital theory
3.3.1 H
2
+
Schrödinger 方程的求解(The solution of the Schrödinger equation of H
2
+
3.3.2 共价键本质的探讨(Discussion on the essence of covalent bond
3.3.3 分子轨道理论要点(Molecular orbital theory
3.3.4 分子轨道的类型(Types of molecular orbitals
3.3.5 第二周期双原子分子的组态(Configuration of period 2 diatomic molecules
(1) 同核双原子分子(Homonuclear diatomic molecules
(2) 异核双原子分子(Heteronuclear diatomic molecules
相关文段 3.1 化学模拟生物固氮(BOX 3.1 Chemical modeling of biological nitrogen fixation
相关文段 3.2 O
2
, N
2
, and NO 的生物化学活性(BOX 3.2 The biochemical reactivity of O
2
, N
2
, and NO
Lecture 8: Valence bond theory (2 units)
3.4 价键理论(Valence bond theory
3.4.1 H
2
Schrödinger 方程的求解(The solution of the Schrödinger equation of H
2
3.4.2 电子配对法(Electron-pairing method
(1) 空间波函数(Spatial wavefunction
(2) 单重态和三重态(Singlet and triplet states
(3) 完全波函数(Total wavefunction
3.4.3 原子轨道的杂化(Hybridization of atomic orbitals
3.5 双原子分子的谱项(Terms symbols of diatomic molecules
7
3.5.1 分子谱项与支项(Terms and levels
3.5.2 非等价组态的谱项(Terms from non-equivalent configuration
3.5.3 等价组态的谱项(Terms from equivalent configuration
Lecture 9: Molecular symmetry and group theory (2 units)
4. 分子对称性与群论初步(Molecular symmetry and group theory
4.1 对称性概念(The concept on symmetry
4.2 对称操作与对称元素(Operations and symmetry elements
4.2.1 旋转与旋转轴(Rotation and rotation axis
4.2.2 反映与镜面(Reflection and mirror plane
4.2.3 反演与对称中心(Inversion and center of inversion
4.2.4 旋转反映与映轴(Improper rotation and improper-rotation axis
4.3 分子点群(The point groups of molecules
4.3.1 单轴群(Uniaxial groups
4.3.2 双面群(Dihedral groups
4.3.3 高阶群(Higher order groups
4.3.4 无旋转轴群(No rotating axis group
4.3.5 确定分子点群的流程图(Flow charts for determining point groups of molecules
Lecture 10: Group representation theory r and applications (2 units)
4.4 分子对称性与偶极矩、旋光性的关系
Relation between molecular symmetry with the dipole moment and the opticity
4.4.1 对称性与偶极矩(Molecular symmetry and the dipole moment
4.4.2 对称性与旋光性(Molecular symmetry and the opticity
相关文段 4.1 手性起源之谜(The mystery of the origin of chirality
4.5 群的表示与应用初步(Group representation theory r and applications
4.5.1 群的定义(Definition of group
4.5.2 相似变换与共轭类(Similarity transform and conjugate classes
4.5.3 群的表示与特征标表(Representations and character tables
8
(1) 对称操作方阵与特征标(Symmetrical Operating Matrix and character
(2) 不可约表示(Irreducible representation
(3) 特征标表与对称标记(Character tables and symmetry labels
(4) 直积与约化(Direct product and reduction
(5) 投影算符(Projection operators
4.5.4 群论在化学中的应用实例(Chemical applications of group theory
Lecture 11: The structures of non-conjugated and conjugated molecules (2 units)
5. 多原子分子的结构与性质(The structures and properties of polyatomic molecules
5.1 非金属单质的结构化学:8−N 法则(Structural chemistry of single nonmetals: 8-N rule
5.2 VSEPR 规则(VSEPR rules
5.3 共轭分子与 HMO 法(Conjugated molecules and the HMO method
5.3.1 丁二烯的 HMO 处理(The HMO treatment of butadiene
5.3.2 直链和单环共轭体系本征值的图解法
Graphic solutions of eigenvalues for straight chain and single-ring conjugated systems
5.3.3 分子图:π电子密度,π键级,自由价(Molecular graph: πelectron density, πbond order,π free valence
5.3.4 共轭效应(Conjugation effect
5.4 正则轨道与定域轨道(CMO and LMO
Lecture 12: The structures of electron-deficient molecules (2 units)
5.5 缺电子分子的结构(The structures of electron-deficient molecules
5.5.1 缺电子原子化合物的三种类型(Three ttypes of the compounds with electron-deficient atoms
5.5.2 硼烷中的多中心键(Multicenter bonds in borane
5.5.3 金属烷基化合物中的多中心键(Multicenter bonds in metal alkyl compounds
Lecture 13: Chemical bond theory of complexes (2 units)
5.6 配合物的化学键理论(Chemical bond theory of complexes
5.6.1 晶体场理论(Crystal field theory
5.6.2 配位场理论(Ligand field theory
5.6.3 T-S 图与电子光谱(Tanabe-Sugano diagrams and the electronic spectra
9
Lecture 14: The Conservation of orbital symmetry (2 units)
5.7 分子轨道对称性守恒原理(Conservation of orbital symmetry
5.7.1 前线轨道理论(Frontier orbitals theory
5.7.2 相关图理论(Relevance graph theory
Lecture 15: Rotational spectra (2 units)
6. 结构分析原理(The principles of structural analysis
6.1 分子中的量子化能级(Quantized energy levels of molecules
6.2 分子光谱(Molecular spectroscopy
6.2.1 双原子分子的转动光谱(Rotational spectra of diatomic molecules
(1) 转动惯量 Moments of inertia
(2) 转动能级(The rotational energy levels
(3) 微波谱(Microwave spectra
(4) 由微波谱计算键长(Calculation of bond length from Microwave spectra
(5) 转动 Raman 光谱(Rotational Raman spectra
(6) Raman 光谱计算键长(Calculation of bond length from Raman spectra
6.2.2 多原子分子的转动光谱(Rotational spectra of polyatomic molecules
(1) 惯量椭球与主轴的选择(Ellipsoid of inertia and selection of principal axis
(2) 刚性转子的类型(Types of Rigid Rotors
(3) 各类陀螺的转动惯量(Moments of inertiab of various gyroscopes
(4) 各类转子的能级和谱项(Energy levels and terms of various rotors
Lecture 16: Vibrational spectra and Electronic spectra (2 units)
6.2.3 双原子分子振动光谱(Vibrational spectra of diatomic molecules
(1) 谐振子的能级和波函数(The energy levels and the wavefunctions of harmonic oscillator
(2) 谐振子的跃迁选律与振动光谱(Selection rules and vibrational spectra of harmonic oscillator
(3) 非谐性的跃迁选律与振动光谱(Selection rules and vibrational spectra of anharmonic oscillator
(4) -转红外光谱(Vibration–rotation Infrared absorption spectra
(5) - Raman 光谱(Vibration–rotation Raman spectra
10
6.2.4 多原子分子振动光谱(Vibrational Spectra of polyatomic molecules
(1) 正则模式(Normal modes
(2) 互斥规则(Exclusive rule
(3) 红外光谱( Infrared absorption spectra
相关文段 6.1 星际物质的转动和振动光谱
BOX 6.1: Rotational and vbrational spectroscopy of interstellar species
6.2.5 电子光谱(Electronic spectra
6.2.6 荧光和磷光(Fluorescence and phosphorescence
相关文段 6.2 绿色荧光蛋白(Green fluorescent protein
Lecture 17: Nuclear magnetic resonance spectra (2 units)
6.3 核磁共振谱(Nuclear magnetic resonance spectra
6.3.1 核磁能级(The energies of nuclei in magnetic fields
6.3.2 核磁共振(Nuclear magnetic resonance
6.3.3 化学位移(The chemical shift
6.3.4 自旋耦合与自旋分裂(Spin coupling and spin splitting
6.3.5 一级谱的简单规律性(Simple regularity of first-order spectra
Lecture 18: Electron paramagnetic resonance spectra and Electron spectroscopy (2 units)
7.4 电子顺磁共振谱(Electron paramagnetic resonance spectra
7.4.1 电子自旋磁能级(The energies of electrons in magnetic fields
7.4.2 顺磁共振(Electron paramagnetic resonance
7.4.3 g 值(The g-value
7.4.4 超精细结构(Hyperfine structure
7.4.5 EPR 的应用(Application of EPR
相关文段 7.2 自旋探针(Spin probes
7.5 电子能谱(Electron spectroscopy
7.5.1 基本原理(The basic principles
7.5.2 仪器(The spectrometer
11
7.5.3 紫外光电子能谱(The Ultraviolet photoelectron spectra
7.5.4 X 射线光电子能谱(The X-ray photoelectron spectra
7.5.5 Auger 能谱(The Auger spectra
Lecture 19: The periodicity and lattices of crystals (2 units)
8. 晶体的点阵结构与 X 射线衍射法(Crystal lattices and X-ray crystallography
8.1 晶体的性质与结构特征(The properties and structural characteristics of crystals
8.2 现代科技中的晶体材料(Crystal materials in modern science and technology
8.3 晶体结构的周期性和点阵(The periodicity and lattices of crystals
8.3.1 结构基元与点阵(Structural motif and lattices
8.3.2 点阵单位和晶格(Lattice units and lattices
8.3.3 平移群(Translation group
8.3.4 晶胞(Cell
Lecture 20: Symmetry of crystals (2 units)
8.4 晶体结构的对称性(Symmetry of crystals
8.4.1 对称操作和对称元素(Symmetry operations and symmetry elements
8.4.2 32 种晶体学点群(32 Crystallographic point groups
8.4.3 7 种晶系和 6 种晶族(7 Crystal systems and 6 crystal families
8.4.4 14 种空间点阵型式(The fourteen Bravais lattices
8.4.5 点阵点、直线点阵、平面点阵的指标(Indices of points, lines and planes in lattice
Lecture 21: The Laue equation set and the Bragg equation (2 units)
8.4.6 空间群(space group
8.4.7 晶体的各种对称性的关系(Relations of various symmetries of crystals
8.5 X 射线衍射法(X-ray diffraction
8.5.1 晶体对 X 射线的相干散射(Coherent scattering of X-ray by crystal
8.5.2 衍射方向与晶胞参数(Diffraction directions and cell parameters
(1) Laue 方程(The Laue equation set
(2) Bragg 方程(The Bragg equation
12
Lecture 22: Powder X-ray diffraction and four-circle diffraction (2 units)
8.5.3 衍射强度与晶胞中原子分布(Diffraction intensity and atomic distribution in unit cell
8.5.4 粉末衍射(Powder X-ray diffraction
8.5.6 倒易点阵与四圆衍射原理(Reciprocal lattice and four-circle diffraction
(1) 倒易点阵(Reciprocal lattice
(2) Ewald 方程(The Ewald equation
(3) 四圆衍射(Four-circle diffraction
Lecture 23: The structures of metallic solids (2 units)
9. 金属晶体与离子晶体的结构(The structures of metallic and ionic solids
9.1 金属单质的晶体结构(The structures of single metal
9.1.1 等径圆球最密堆积结构:A
1
A
3
Closest packing of equal diameter spheres: A
1
and A
3
9.1.2 最密堆积中的空隙类型(Holes in closest-packed structures
9.1.3 非最密堆积结构(Nonclosest-packed structures
9.1.4 空间利用率(The spatial utilization rate
9.1.5 金属原子半径(Atomic radii of metals
Lecture 24: The structures of ionic solids (2 units)
9.2 离子晶体的结构和性质(Structures and properties of ionic solids
9.2.1 离子键和晶格能(Ionic bonds and lattice enthalpy
9.2.2 离子半径(Radii of ions
9.2.3 离子半径比与配位数(The ratio of ionic radii and coordination numbers
9.2.4 离子堆积与晶体结构(Ionic packing and crystal structures
9.2.5 二元离子晶体的结晶化学规律(Crystallization chemistry of binary Ionic solids
Lecture 25: Crystallochemistry of multicomponent ionic solids (2 units)
9.2.6 多元离子晶体的结晶化学规律: Pauling 规则
Crystallochemistry of multicomponent ionic solids: Pauling rules
9.2.7 硅酸盐的结构简介(The introduction to the structures of silicates
9.2.8 钙钛矿型结构(The structures of perovskite type
13
9.2.9 离子极化效应(The ionic polarization effects
9.2.10 结晶化学定律与键型变异原理(Crystal chemical law and bond-type variation principle
Lecture 26-30: The rates of chemical reactions (11 units)
Empirical chemical kinetics
10.1 The rates of reactions
10.2 Integrated rate laws
10.3 Reactions approaching equilibrium
10.4 The temperature dependence of reaction rates
Accounting for the rate laws
10.5 Elementary reactions
10.6 Complex reactions
The kinetics of complex reactions
10.7 Chain reactions
10.7.1 The rate laws of chain reactions
10.7.2 Explosions
10.8 Polymerization kinetics
10.9 Enzyme Catalysis
10.10 Photochemistry: kinetics of photophysical and photochemical processes
Lecture 31-32: Molecular reaction dynamics (3 units)
11.1 Collision theory
11.2 Transition state theory
11.2.1 The Eyring equation
11.2.2 Thermodynamic aspects
11.2.3 Potential energy surfaces
18.
教材及其它参考资料 Textbook and Supplementary Readings
教材 (Textbook)
1. Physical Chemistry, P.W. Atkins, Seventh Edition (required)
2. 结构化学,李炳瑞,第 3 版或第 2 版,高等教育出版社
参考书 (Reference)
14
1. Solutions Manual for Physical Chemistry, 7th edition, Atkins et al.(recommended)
2. 结构化学学习指导与习题解答,李炳瑞,高等教育出版社
3. Survival Guide for Physical Chemistry, M. Francl (recommended)
课程评估 ASSESSMENT
19.
评估形式
Type of
Assessment
评估时间
Time
占考试总成绩百分比
% of final
score
违纪处罚
Penalty
备注
Notes
出勤 Attendance
课堂表现
Class
Performance
小测验
Quiz
课程项目 Projects
平时作业
Assignments
30
期中考试
Mid-Term Test
30
期末考试
Final Exam
40
期末报告
Final
Presentation
其它(可根据需
改写以上评估方
式)
Others (The
above may be
modified as
necessary)
20.
记分方式 GRADING SYSTEM
A. 十三级等级制 Letter Grading
B. 二级记分制(通/不通过) Pass/Fail Grading
课程审批 REVIEW AND APPROVAL
21.
本课程设置已经过以下责任人/员会审议通过
This Course has been approved by the following person or committee of authority
化学系教学指导委员会
Teaching committee of the chemistry department