This grant from the Organic Dynamics Program supports the continuing work of Dr. Przemyslaw B. Maslak at the Pennsylvania State University. The results of this investigation will provide an improved understanding of the relationships between chemical reactivity and electronic and molecular structure fora highly reactive class of chemical intermediates. The experiments that will be carried out by Dr. Maslak will focus on the unimolecular cleavage of radical ions into radicals and ions, a processes called mesolysis. Kinetic and thermodynamic parameters will be determined for mesolytic cleavage reactions of sigma bonds in a series of radical ions that can be generated by photoinduced electron transfer. Standard redox potentials will be measured for corresponding radicals, ions, and radical ions. Experiments will probe the effects of molecular structure, ion pairing, and solvent on the relationship between activation energy for mesolytic cleavage and the corresponding free energy change for bond rupture.
