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Overview
The authors' goal is the presentation of the three major areas of phys ical chemistry: molecular structure, the equilibrium properties of sys tems, and the kinetics of transformations of systems. The theoretical foundations of these subjects are, respectively, quantum mechanics, th ermodynamics and equilibrium statistical mechanics, and chemical kinet ics and kinetic theory. These theories, firmly based on experimental f indings, constitute the structure required for the understanding of pa st accomplishments and the basis for recognition and development of si gnificant new areas in physical chemistry.
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Stanford University
Table of Contents
Preface
PART I: THE STRUCTURE OF MATTER
1. The Microscopic World: Atoms and Molecules
1.1. Development of the Atomic Theory: Relative Atomic Weights
1.2. Atomic Magnitudes
1.3. The ChargetoMass Ratio of the Electron: Thomson's Method
1.4. The Charge of the Electron: Millikan's Method
1.5. Mass Spectrometry
1.6. The Atomic Mass Scale and the Mole
1.7. The Periodic Table
2. Origins of the Quantum Theory of Matter
2.1. The FranckHertz Experiment
2.2. The Photoelectric Effect
2.3. Xrays and Matter
2.4. The Emission Spectra of Atoms
2.5. The Nuclear Atom
2.6. The Problem of BlackBody Radiation
2.7. The Concept of Action
2.8. The Harmonic Oscillator
2.9. Action Quantized: The Heat Capacity of Solids
2.10. Some Orders of Magnitude
2.11. Bohr's Model of the Atom
Appendix 2A: Rutherford Scattering
3. Matter Waves in Simple Systems
3.1. The de Broglie Hypothesis
3.2. The Nature of Waves
3.3. Dispersion Relations and Wave Equations: The Free Particle
3.4. Operators
3.5. Eigenfunctions and Eigenvalues
3.6. The Particle in a OneDimensional Box
3.7. The Indeterminacy or Uncertainty Principle
3.8. Expectation Values; Summary of Postulates
3.9. Particles in Two and ThreeDimensional Boxes
3.10. Particles in Circular Boxes
3.11. Particles in Spherical Boxes
3.12. The Rigid Rotor
Appendix 3A: More on Circular Coordinates and the Circular Box
4. Particles in Varying Potential Fields; Transitions
4.1. Finite Potential Barriers
4.2. The Quantum Mechanical Harmonic Oscillator
4.3. The Hydrogen Atom
4.4. The Shapes of Orbitals
4.5. Transitions between Energy Levels
5. The Structure of Atoms
5.1. Electron Spin; Magnetic Phenomena
5.2. The Pauli Exclusion Principle; the Aufbau Principle
5.3. Electronic Configurations of Atoms
5.4. Calculation of Atomic Structures
5.5. Atomic Structure and Periodic Behavior
5.6. Term Splitting and the Vector Model
5.7. Fine Structure and SpinOrbit Interactions
Appendix 5A: The SternGerlach Experiment
6. The Chemical Bond in the Simplest Molecules: H2+ and H2
6.1. Bonding Forces between Atoms
6.2. The Simplest Molecule: The Hydrogen MoleculeIon, H2+
6.3. H2+: Molecular Orbitals and the LCAO Approximation
6.4. H2+: Obtaining the Energy Curve
6.5. H2+: Correlation of Orbitals; Excited States
6.6. The H2 Molecule: Simple MO Description
6.7. Symmetry Properties of Identical Particles
6.8. H2: The Valence Bond Representation
6.9. H2: Beyond the Simple MO and VB Approximations
6.10. H2: Excited Electronic States
Appendix 6A: Orthogonality
Appendix 6B: Hermitian Operators
7. More About Diatomic Molecules
7.1. Vibrations of Diatomic Molecules
7.2. Rotations of Diatomic Molecules
7.3. Spectra of Diatomic Molecules
7.4. The Ionic Bond
7.5. Homonuclear Diatomic Molecules: Molecular Orbitals and Orbital Correlation
7.6. Homonuclear Diatomic Molecules: Aufbau Principle and Structure of FirstRow Molecules
7.7. Introduction to Heteronuclear Diatomic Molecules: Electronegativity
7.8. Bonding in LiH: Crossing and Noncrossing Potential Curves
7.9. Other FirstRow Diatomic Hydrides
7.10. Isoelectronic and Other Series
Appendix 7A: Perturbation Theory
8. Triatomic Molecules
8.1. Electronic Structure and Geometry in the Simplest Cases: H3 and H3+
8.2. Dihydrides: Introduction to the Water Molecule
8.3. Hybrid Orbitals
8.4. Delocalized Orbitals in H2O: The General MO Method
8.5. Bonding in More Complex Triatomic Molecules
8.6. Normal Coordinates and Modes of Vibration
8.7. A Solvable Example: The Vibrational Modes of CO2
8.8. Transitions and Spectra of Polyatomic Molecules: Rotations and Vibrations
8.9. Transitions and Spectra of Polyatomic Molecules: Magnetic Transitions
8.10. Transitions and Spectra of Polyatomic Molecules: Electronic Transitions
9. Larger Polyatomic Molecules
9.1. Small Molecules
9.2. Catenated Carbon Compounds; Transferability
9.3. Other Extended Structures
9.4. Some Steric Effects
9.5. Complex Ions and Other Coordination Compounds: Simple Polyhedra
9.6. Chirality and Optical Rotation
9.7. Chiral and Other Complex Ions
9.8. Magnetic Properties of Complexes
9.9. Electronic Structure of Complexes
Appendix 9A: Schmidt Orthogonalization
10. Intermolecular Forces
10.1. LongRange Forces: Interactions between Charge Distributions
10.2. Empirical Intermolecular Potentials
10.3. Weakly Associated Molecules
11. The Structure of Solids
11.1. Some General Properties of Solids
11.2. Space Lattices and Crystal Symmetry
11.3. Xray Diffraction from Crystals: The Bragg Model
11.4. The Laue Model
11.5. Determination of Crystal Structures
11.6. Techniques of Diffraction
11.7. Molecular Crystals
11.8. Structures of Ionic Crystals
11.9. Binding Energy of Ionic Crystals
11.10. Covalent Solids
11.11. The FreeElectron Theory of Metals
11.12. The Band Theory of Solids
11.13. Conductors, Insulators, and Semiconductors
11.14. Other Forms of Condensed Matter
PART II: MATTER IN EQUILIBRIUM: STATISTICAL MECHANICS AND THERMODYNAMICS
12. The Perfect Gas at Equilibrium and the Concept of Temperature
12.1. The Perfect Gas: Definition and Elementary Model
12.2. The Perfect Gas: A General Relation between Pressure and Energy
12.3. Some Comments about Thermodynamics
12.4. Temperature and the Zeroth Law of Thermodynamics
12.5. Empirical Temperature: The Perfect Gas Temperature Scale
12.6. Comparison of the Microscopic and Macroscopic Approaches
13. The First Law of Thermodynamics
13.1. Microscopic and Macroscopic Energy in a Perfect Gas
13.2. Description of Thermodynamic States
13.3. The Concept of Work in Thermodynamics
13.4. Intensive and Extensive Variables
13.5. Quasistatic and Reversible Processes
13.6. The First Law: Internal Energy and Heat
13.7. Some Historical Notes
13.8. Microscopic Interpretation of Internal Energy and Heat
13.9. Constraints, Work, and Equilibrium
14. Thermochemistry and Its Applications
14.1. Heat Capacity and Enthalpy
14.2. Energy and Enthalpy Changes in Chemical Reactions
14.3. Thermochemistry of Physical Processes
14.4. Introduction to Phase Changes
14.5. Standard States
14.6. Thermochemistry of Solutions
14.7. Molecular Interpretation of Physical Processes
14.8. Bond Energies
14.9. Some Energy Effects in Molecular Structures
14.10. Lattice Energies of Ionic Crystals
15. The Concept of Entropy: Relationship to the EnergyLevel Spectrum of a System
15.1. The Relationship between Average Properties and Molecular Motion in an NMolecule System: Time Averages and Ensemble Averages
15.2. Ensembles and Probability Distributions
15.3. Some Properties of a System with Many Degrees of Freedom: Elements of the Statistical Theory of Matter at Equilibrium
15.4. The Influence of Constraints on the Density of States
15.5. The Entropy: A Potential Function for the Equilibrium State
Appendix 15A: Comments on Ensemble Theory
Appendix 15B: *W(E) as a System Descriptor
Appendix 15C: The Master Equation
16. The Second Law of Thermodynamics: The Macroscopic Concept of Entropy
16.1. The Second Law of Thermodynamics
16.2. The Existence of an Entropy Function for Reversible Processes
16.3. Irreversible Processes: The SecondLaw Interpretation
16.4. The Clausius and Kelvin Statements Revisited
16.5. The Second Law as an Inequality
16.6. Some Relationships between the Microscopic and Macroscopic Theories
Appendix 16A: PoincarĂ© Recurrence Times and Irreversibility
17. Some Applications of the Second Law of Thermodynamics
17.1. Choice of Independent Variables
17.2. The Available Work Concept
17.3. Entropy Changes in Reversible Processes
17.4. Entropy Changes in Irreversible Processes
17.5. Entropy Changes in Phase Transitions
18. The Third Law of Thermodynamics
18.1. The Magnitude of the Entropy at T=0
18.2. The Unattainability of Absolute Zero
18.3. Experimental Verification of the Third Law
19. The Nature of the Equilibrium State
19.1. Properties of the Equilibrium State of a Pure Substance
19.2. Alternative Descriptions of the Equilibrium State for Different External Constraints
19.3. The Stability of the Equilibrium State of a OneComponent System
19.4. The Equilibrium State in a Multicomponent System
19.5. Chemical Equilibrium
19.6. Thermodynamic Weight: Further Connections between Thermodynamics and Microscopic Structure
19.7. An Application of the Canonical Ensemble: The Distribution of Molecular Speeds in a Perfect Gas
20. An Extension of Thermodynamics to the Description of Nonequilibrium Processes
20.1. General Form of the Equation of Continuity
20.2. Conservation of Mass and the Diffusion Equation
20.3. Conservation of Momentum and the NavierStokes Equation
20.4. Conservation of Energy and the Second Law of Thermodynamics
20.5. Linear Transport Processes
20.6. Negative Temperature
20.7. Thermodynamics of Systems at Negative Absolute Temperature
Appendix 20A: Symmetry of the Momentum Flux Tensor
21. The Properties of Pure Gases and Gas Mixtures
21.1. Thermodynamic Description of a Pure Gas
21.2. Thermodynamic Description of a Gas Mixture
21.3. Thermodynamic Description of Gaseous Reactions
21.4. An Example: The Haber Synthesis of NH3
21.5. Statistical Molecular Theory of Gases and Gas Reactions
21.6. The Statistical Molecular Theory of the Equilibrium Constant
21.7. The Statistical Molecular Theory of the Real Gas
Appendix 21A: Influence of Symmetry of the Wave Function on the Distribution over States: FermiDirac and BoseEinstein Statistics
Appendix 21B: Symmetry Properties of the Molecular Wave Function: Influence of Nuclear Spin on the Rotational Partition Function
Appendix 21C: The Semiclassical Partition Function; The Equation of State of an Imperfect Gas
22. Thermodynamic Properties of Solids
22.1. Differences between Gases and Condensed Phases
22.2. The Influence of Crystal Symmetry on Macroscopic Properties
22.3. Microscopic Theory of the Thermal Properties of Crystalline Solids
22.4. The Contribution of Anharmonicity to the Properties of a Crystal
22.5. Some Properties of Complex Solids and of Imperfect Solids
22.6. Electronic Heat Capacity of Metals
Appendix 22A: Evaluation of FermiDirac Integrals
23. Thermodynamic Properties of Liquids
23.1. Bulk Properties of Liquids
23.2. The Structure of Liquids
23.3. Relationships between the Structure and the Thermodynamic Properties of a Simple Liquid
23.4. The Molecular Theory of Monoatomic Liquids: General Remarks
23.5. The Molecular Theory of Monoatomic Liquids: Approximate Analyses
23.6. The Molecular Theory of Polyatomic Liquids
Appendix 23A: Xray Scattering from Liquids: Determination of the Structure of a Liquid
Appendix 23B: Functional Differentiation
24. Phase Equilibria in OneComponent Systems
24.1. General Survey of Phase Equilibria
24.2. Thermodynamics of Phase Equilibria in OneComponent Systems
24.3. Phase Transitions Viewed as Responses to Thermodynamic Instabilities
24.4. The Statistical Molecular Description of Phase Transitions
Appendix 24A: The Scaling Hypothesis for Thermodynamic Functions
Appendix 24B: Aspects of Density Functional Theory
25. Solutions of Nonelectrolytes
25.1. The Chemical Potential of a Component in an Ideal Solution
25.2. The Chemical Potential of a Component in a Real Solution
25.3. Partial Molar Quantities
25.4. LiquidVapor Equilibrium
25.5. LiquidSolid Equilibrium
25.6. The Colligative Properties of Solutions: BoilingPoint Elevation, FreezingPoint Depression, and Osmotic Pressure
25.7. Chemical Reactions in Nonelectrolyte Solutions
25.8. More about Phase Equilibrium in Mixtures
25.9. Critical Phenomena in Mixtures
25.10. The Molecular Theory of Solutions of Nonelectrolytes
26. Equilibrium Properties of Solutions of Electrolytes
26.1. The Chemical Potential
26.2. Cells, Chemical Reactions, and Activity Coefficients
26.3. Comments on the Structure of Water
26.4. The Influence of Solutes on the Structure of Water
26.5. The Statistical Mechanics of Electrolyte Solutions
26.6. Molten Salts and Molten Salt Mixtures
26.7. The Structure of an Electrolyte Solution Near an Electrode
PART III: PHYSICAL AND CHEMICAL KINETICS
27. Molecular Motion and Collisions
27.1. Kinematics
27.2. Forces and Potentials
27.3. Collision Dynamics
27.4. Types of Collisions
27.5. Scattering Cross Sections
27.6. Elastic Scattering of Hard Spheres
27.7. Elastic Scattering of Atoms
27.8. Quantum Mechanical Scattering
28. The Kinetic Theory of Gases
28.1. Distribution Functions
28.2. Collision Frequency in a Dilute Gas
28.3. The Evolution of Velocity Distributions in Time
28.4. The MaxwellBoltzmann Distribution
28.5. Collision Frequency for HardSphere Molecules
28.6. Molecular Fluxes of Density, Momentum Density, and Energy Density
28.7. Effusion
28.8. Transport Properties of Gases
28.9. Energy Exchange Processes
28.10. Sound Propagation and Absorption
29. The Kinetic Theory of Dense Phases
29.1. Transport Properties in Dense Fluids
29.2. Some Basic Aspects of Brownian Motion
29.3. Stochastic Approach to Transport
29.4. Autocorrelation Functions and Transport Coefficients
29.5. Transport in Solids
29.6. Electrical Conductivity in Electrolyte Solutions
30. Chemical Kinetics
30.1. General Concepts of Kinetics
30.2. Interactions between Reactive Molecules
Vignette: Quantum Mechanical Computations of Potential Energy Hypersurfaces, by H.F. Schaefer
30.3. Collisions between Reactive Molecules
Vignette: FemtochemistryReaction Dynamics with Atomic Resolution, by A.H. Zewail
30.4. HardSphere Collision Theory: Reactive Cross Sections
30.5. HardSphere Collision Theory: The Rate Coefficient
30.6. ActivatedComplex Theory
Vignette: Present Day View of Transition State Theory, by D.G. Truhlar
30.7. ActivatedComplex Theory: Thermodynamic Interpretation
30.8. Theory of Reaction Kinetics in Solution
Vignette: Kramers' Theory of Reactions in Solutions, by M.O. Vlad and J. Ross
Vignette: Chemical Reactions in Condensed Phases, by P.G. Wolynes
30.9. Linear FreeEnergy Relationships
30.10. Experimental Methods in Kinetics
30.11. Analysis of Data for Complex Reactions
30.12. Mechanisms of Chemical Reactions
30.13. Bimolecular Reactions
Vignette: Electron Transfer Reactions, by R.A. Marcus
30.14. Unimolecular Reactions
30.15. Termolecular Reactions
31. Some Advanced Topics in Chemical Kinetics
31.1. More about Unimolecular Reactions
31.2. Kinetics of Photochemically Induced Reactions
31.3. Chain Reactions
31.4. Nonlinear Phenomena
31.5. Fluctuations in Chemical Kinetics
31.6. Symmetry Rules for Chemical Reactions
31.7. Introduction to Catalysis
31.8. Enzyme Catalysis
31.9. AcidBase Catalysis
31.10. MetalIon Complex and Other Types of Homogeneous Catalysis
31.11. Heterogeneous Reactions: Adsorption of Gas on a Surface
31.12. Heterogeneous Catalysis
31.13. Kinetics of Electrode Reactions (a Vignette by C.E.D. Chidsey)
Vignette: Applications of Physical Chemistry: A Biological Example, by B. Eisenberg
Appendices
II. Partial Derivatives
III. Glossary of Symbols
IV. Searching the Scientific Literature
Index
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