Electronic States of Molecules and Atom Clusters

Inhaltsverzeichnis

• 1. Models and concepts in molecular theory.
• 1.1 Scope of the quantum theory of molecules.
• 1.2 Born Oppenheimer states.
• 1.3 Computational and interpretational problems.
• 1.4 Rôle and limitations of simplified models.
• 1.5 Simplified models and model Hamiltonians.
• 1.6 Atoms in molecules and electronegativities.
• 1.7 A conclusion: Models and the Plague of Non-observables.
• 2. Mathematical foundations.
• 2.1 Mathematical construction of many-electron models from an orbital basis.
• 2.2 Model Hamiltonians.
• 2.3 Matrix formalism. Inclusion of overlap.
• 2.4 The spectral decomposition of the Hamiltonian and effective potentials.
• 3. One-electron schemes.
• 3.1 Hückel-type methods.
• 3.2 A ‘naive’ method for ? electrons.
• 3.3 The Hückel method for all valence-electrons: The tight binding (TB) approach of solid-state physics.
• 3.4 All-valence-electron treatments: The extended Hückel theory (EHT).
• 4. Simplified SCF one-electron schemes and beyond.
• 4.1 The SCF Hamiltonian.
• 4.2 Construction of non-SCF Hamiltonians.
• 4.3 Many-electron models and their SCF version.
• 4.4 Methods with iterative determination of atomic parameters.
• 4.6 A general form of all valence SCF methods: The SCF extended-Hückel method.
• 4.7 Beyond one-electron schemes. Correlation, PCILO method excited states.
• 4.8 A case study in semiempirical computations: Molecular force fields.
• 4.9 Limitations of semiempirical and limited-basis methods: The N2O4 molecule.
• 5. The basis problem.
• 5.1 MVAO basis.
• 5.2 Non-orthogonality.
• 5.3 General orbital bases.
• 5.4 ?-Electron models and the ?-? separation.
• 5.5 Basis problem in solid-state physics.
• 5.6 Metal-metal bond and the X? method.
• 5.7 Reliability of computations and choice of the orbital basis.
• 5.8 A comment on the use of group theory incalculations on molecules and aggregates of atoms.