Electronic structure and Chemical bond. Electronic control of nuclear configuration:easyjet vibrations and vibronic coupling. Electronic structure investigated by Physical methods. Stereochemistry and Crystal Chemistry. Electron Transfer, Redox properties, and Electron-Conformational effects. Reactivity and Catalysis.
“Electronic Structure and Properties of Transition Metal Compounds”, Isaac Bersuker, Wiley-Interscience 1996; “Transition Metal Chemistry”, M. Gerloch and E.C Constable, VCH, 1994; “Orbital Interactions in Chemistry”, T.A. Albright. J.K. Burdett, and M-H Whangbo Wiley-interscience 1985; “Physical Methods for Chemists”, R.S. Drago, Saunders College Publishing, 1992
Learning Objectives
The student will be able to interpret the spectra obtained with the several techniques of investigation on the basis of the electronic structure of the metal complexes under study. The student will be able to make expectations on their reactivity. At the end of the course the student will have a general view on the theory of the structural and electronic properties of coordination compounds containing transition metal ions. The student will be able to design characterization strategies for new systems.
Prerequisites
Courses required: none
Courses recommended: Physical Chemistry II and Inorganic Chemistry
Teaching Methods
Total number of hours for Lectures (hours): 48
Type of Assessment
Oral exam.
Course program
1. Electronic Structure and the Chemical Bond 1.1 Role of d and f electrons in the coordination bond 1.2 Electronic Configurations and related qualitative aspects 1.3 Ligands: bond 1.4 Energies, geometries and Charge distributions 1.5 Relativistic effects
2. Electronic Control of the nuclear configuration: Vibrations and Vibronic coupling 2.1 Molecular Vibrations 2.2 Vibronic Coupling 2.3 Jahn-Teller Effect
3. Electronic Structure Investigated by Physical Methods 3.1 Electronic Spectra 3.2 d-d Transitions 3.3 X-ray and Ultraviolet 3.4 Magnetic Properties 3.5 Determination of Electron Charge and Spin Density
4. Stereochemistry and Crystal Chemistry 4.1 Semiclassical model 4.2 Vibronic Stereochemistry 4.3 Mutual influence of Ligands 4.4 Crystal Stereochemistry
5. Electron Transfer. Redox Properties and Electron-Conformational Effects 5.1 Electron Transfer and Charge Transfer 5.2 Electron Transfer in Mixed-Valence Compounds
6. Reactivity and catalytic Action 6.1 Electronic Factors in Reactivity 6.2 Electronic Control of Chemical Activation via Vibronic Couplimg 6.3 Direct Computation of Energy Barriers of Chemical Reactions