Our overall aim is to study photochemical mechanisms and to develop new photochemical mechanistic methodology. Among the specific problems to be investigated are the following: (1) A study of some allene rearrangements which appear parallel to ( ) ketone counterparts ( ), (2) a search for the mirror image process, where a ( ) excited is involved, (3) completion of the synthesis and study of bugatriyne, a bicyclic Mobius type of molecule with three acetylenic bridges, (4) synthesis and study of the hexa-yne relative of bugatriyne, (5) use of chiral quenchers to determine whether species along the reaction coordinate are subject to energy transfer, (6) continuation of our efforts on solid state photochemistry and means of controlling the solid state medium, (7) investigation of hypersurfaces for many of the reactions we have studied, including a comparison of the theoretical methods, (8) continuing our energy transfer studies using the rod-like molecules we have synthesized to ascertain if we really do have sigma exciton transfer, (9) utilization of bond-oriented basis set orbitals in SCF_CI calculations to give results meaningful to organic chemical studies, (10) testing of our ( ) treatment to our quantum mechanical results to assess energy localization and diffusion during photochemical reaction, (11) exploration of the "Mechanism C" triplet rearrangement of vinylcyclopropenes to determine regioselectivity and to uncover the mechanisms of the diradical ring expansions, (12) determination of the mechanism of rearrangement of the acylcyclopropenes as well as imine and thione relatives, (13) investigation of the generality and sources of "Exchange Integral Control" of reaction multiplicity, (14) development of new photochemical concepts.
