Photoprocesses in Transition Metal Complexes, Biosystems and Other Molecules. Experiment and Theory

The scope of this paper is to recall fundamental notions of the molecular spectroscopy and dynamics, necessary for discussion of photophysical and photochemical processes in condensed phases. We will thus treat in a more detailed way the specific features which are important for molecular systems strongly interacting with their environment. Other aspects such as the time evolution of isolated molecules, single-level excitation and state-to-state chemistry, important for the gas-phase photophysics are omitted. We start (Sec.2) with a brief description of radiative processes (light absorption and emission) in molecules. In the quantum-mechanical treatment of this problem, the appropriate basis is that of so-called zero-order states, corresponding to the traditional scheme of electronic states (singlets, doublets, triplets etc.) and vibrational levels belonging to each state. The important point will be deduction of selection rules for most radiative transitions. At this stage all molecular states are considered as stationary states. In order to treat the breakdown of simple selection rules and non-radiative transitions between individual molecular states, it is necessary to take into account the mechanisms coupling the zero-order states (Sec.3). We will first focus on intramolecular coupling effects and then discuss the solvent effects on intramolecular relaxation processes. The problem of the non-radiative transfer of the electronic energy between different molecules - closely related to that of the energy dissipation within a single molecule will be treated in Sec.4.

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The main emphasis in this book is on the photoprocesses of transition metal complexes and biosystems, but not to the exclusion of other photoprocesses. The book will thus be useful to a wide range of researchers. Beginning with a basic introduction to photophysics, quantum chemistry, and the spectroscopic techniques used for the study of organometallic intermediates and biliproteins, the book goes on to discuss the photochemistry of organometallics, special attention being paid to the photochemistry of metalbonded carbonyls and polynuclear systems in supramolecular photochemistry. br/ After moving to a discussion of large systems, the book then developes some aspects of the photophysics of biosystems, before closing with a discussion of artificial photosynthetic model systems. br/

Contenu
Elementary Notions of Photophysics.- Theory of Electron Transfer Reactions and Comparison with Experiments.- Calculation of the Lifetime of Molecules in Electronically Excited States.- Relativistic Effects in Molecular Calculations.- Spectroscopic Techniques for Organometallic Intermediates.- Photochemistry Involving Cr(Co)S - Still Some Puzzles.- Photochemistry of Organo-Metal Carbonyls: Stereochemical and Catalytic Aspects.- Photochemistry of Organometalllcs: Quantum Chemical Approach.- Photochemistry of Metal-Metal Bonded Carbonyls and its Relationship to Electron Transfer Chain Catalysis.- Supramolecular Photochemistry: Antenna Effect in Polynuclear Metal Complexes.- Photophysics of Polynuclear Complexes. Intercomponent Energy and Electron Transfer Processes.- Rigid Alkane-Bridged Donor-Acceptor Systems as Tools for the Investigation of Solvent -, Distance -, and Conformation-Effects in Electron Transfer Processes.- Spectroscopy of Biliproteins and Energy Transfer in Photosynthetic Antenna Complexes.- Photosynthesis: Biological Conversion of Light into Chemical Energy.- Testing Primary Charge Separation in Photosynthetic Reaction Centers with External Electric Fields.- Examining Long-Distance Biological Electron Transfer with Synthetic Model Systems.- Tutorial Work: a Miscellany of AB Initio Quantum Chemistry. the Helium Atom Studied by Various Methods.- Posters.- List of Contributors.- List of Participants.