Molecular Orbitals and Organic Chemical Reactions is both a simplified account of molecular orbital theory and a review of it 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 serves in a sense as a second edition of the author s influential earlier book Frontier Orbitals and Organic Chemical Reactions, but has been completely rewritten, greatly enlarging the chapters on molecular orbital theory itself, and on the theoretical basis for the principle of hard and soft acids and bases, and a whole chapter on the stereochemistry of the fundamental organic reactions. Correlation diagrams have been added to the discussion of pericyclic chemistry, and a great deal more in that, the largest chapter. A number of new topics, both omissions from the earlier book and work that has taken place in the intervening years, are included, and there are more words of caution in discussing frontier orbital theory itself.
Molecular Orbitals and Organic Chemical Reactions: Student Edition is an individual textbook on this important subject for student or organic, physical organic and computational chemistry.
1.1 The Orbital Model.
1.2 Mathematical Methods.
1.3 Basic Postulates.
1.4 Physical Interpretation of the Basic Principles.
2.1 Definitions and Elementary Properties.
2.2 Properties of Determinants.
2.3 Special Matrices.
2.4 The Matrix Eigenvalue Problem.
3 Atomic Orbitals.
3.1 Atomic Orbitals as a Basis for Molecular Calculations.
3.2 Hydrogen–like Atomic Orbitals.
3.3 Slater–type Orbitals.
3.4 Gaussian–type Orbitals.
4 The Variation Method.
4.1 Variational Principles.
4.2 Nonlinear Parameters.
4.3 Linear Parameters and the Ritz Method.
4.4 Applications of the Ritz Method.
Appendix: The Integrals J, K, J´ and K´.
5.1 The Zeeman Effect.
5.2 The Pauli Equations for One–electron Spin.
5.3 The Dirac Formula for N–electron Spin.
6 Antisymmetry of Many–electron Wavefunctions.
6.1 Antisymmetry Requirement and the Pauli Principle.
6.2 Slater Determinants.
6.3 Distribution Functions.
6.4 Average Values of Operators.
7 Self–consistent–field Calculations and Model Hamiltonians.
7.1 Elements of Hartree Fock Theory for Closed Shells.
7.2 Roothaan Formulation of the LCAO MO SCF Equations.
7.3 Molecular Self–consistent–field Calculations.
7.4 H uckel Theory.
7.5 A Model for the One–dimensional Crystal.
8 Post–Hartree Fock Methods.
8.1 Configuration Interaction.
8.2 Multiconfiguration Self–consistent–field.
8.3 Møller Plesset Theory.
8.4 The MP2–R12 Method.
8.5 The CC–R12 Method.
8.6 Density Functional Theory.
9 Valence Bond Theory and the Chemical Bond.
9.1 The Born Oppenheimer Approximation.
9.2 The Hydrogen Molecule H2.
9.3 The Origin of the Chemical Bond.
9.4 Valence Bond Theory and the Chemical Bond.
9.5 Hybridization and Molecular Structure.
9.6 Pauling s Formula for Conjugated and Aromatic Hydrocarbons.
10 Elements of Rayleigh Schroedinger Perturbation Theory.
10.1 Rayleigh Schroedinger Perturbation Equations up to Third Order.
10.2 First–order Theory.
10.3 Second–order Theory.
10.4 Approximate E2 Calculations: The Hylleraas Functional.
10.5 Linear Pseudostates and Molecular Properties.
10.6 Quantum Theory of Magnetic Susceptibilities.
Appendix: Evaluation of µ and .
11 Atomic and Molecular Interactions.
11.1 The H H Nonexpanded Interactions up to Second Order.
11.2 The H H Expanded Interactions up to Second Order.
11.3 Molecular Interactions.
11.4 Van der Waals and Hydrogen Bonds.
11.5 The Keesom Interaction.
12.1 Molecular Symmetry.
12.2 Group Theoretical Methods.
12.3 Illustrative Examples.