Structure, interface photochemistry

The reactivity of molecules bound to surfaces, located at various kinds of interfaces, solubilized in microheterogeneous media, or incorporated as "guests" in various "hosts" as inclusion complexes has been the subject of much recent study. Indeed the structure of the medium, the nature of "solubilization sites" and reactivity in these environments have all been the focus of independent or interrelated investigations (1-12). Photochemistry has played a major role in these studies both in terms of studies of the media and also in terms of modified or controlled reactivity (1,5,8,9). In the course of these investigations numerous questions have arisen many of these have developed from differing pictures of solute-environment interactions which are furnished by different studies using different molecules as "probes" (5,10-12). Controversies arising... 

The BOVB method does not of course aim to compete with the standard ab initio methods. BOVB has its specific domain. It serves as an interface between the quantitative rigor of today s capabilities and the traditional qualitative matrix of concepts of chemistry. As such, it has been mainly devised as a tool for computing diabatic states, with applications to chemical dynamics, chemical reactivity with the VB correlation diagrams, photochemistry, resonance concepts in organic chemistry, reaction mechanisms, and more generally all cases where a valence bond reading of the wave function or the properties of one particular VB structure are desirable in order to understand better the nature of an electronic state. The method has passed its first tests of credibility and is now facing a wide field of future applications. 

K.B. Eisenthal, Photochemistry and Photophysics of Liquid Interfaces by Second Harmonic Spectroscopy, J. Phys. Chem. 100 (1996) 12997. (Article among the topics discussed are dynamics of photo-induced structure changes, transport of charge across an interface, the rotational motions of interfacial molecules, intermolecular energy transfer within the interface, interfacial photopol5mieriza-tion, and photoprocesses at a semiconductor/liquid interface,)... 

Any open-surface reaction (such as photochemistry, reactions at gas-liquid interface vaporization and adsorption) yielding or consuming a coloured product will lead to the formation of spatial structures. 

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