Adiabatic Photoreactions of Organic Molecules

An adiabatic photoreaction is a chemical process that occurs entirely on a single excited electronic energy surface. As a rule, most photoreactions of organic molecules start on an excited electronic surface but “jump” to a lower surface somewhere along the reaction coordinate. There are, however, exceptions to this general rule. For example, photoreactions involving small structural changes and minor alterations in covalent bonding ( e.g. , proton transfer and complex formation) are commonly found to occur adiabatically. The purpose of this review is to survey examples of more complicated adiabatic photoreactions such as fragmentation, electrocyclic rearrangements, and geometrical isomerizations. The concepts employed are presented in an introductory discussion.