26th Annual Student Research Conference
Investigation of the unusual stability of peroxyl radical cation conformers
Kallie I. Hilsabeck* and Scotty G. Reynolds
Dr. Eric V. Patterson, Faculty Mentor
The existence of olefin radical cations has been of recent interest, as have their reaction with molecular oxygen. The peroxyl radical cations formed in such a reaction may demonstrate unusual stability. This reaction will be studied for a series of substituted olefins in which one or more olefinic protons are substituted by methyl or phenyl groups. Previously published computational work by others shows that rearrangement of these molecules may depend on the nature of the substituents. However, this previous study used the B3LYP density functional, which is known to be flawed. Our current investigation compares these previous results to the newer and more accurate density functional, M06-2X. The potential energy surfaces for the oxidation and subsequent rearrangements for olefin radical cations with different substituents will be presented, and factors determining their relative stabilities will be examined.
Keywords: olefin radical cations, peroxyl radical cations, density functional, computational, isomerization, rearrangements, stability
Topic(s):Chemistry
Presentation Type: Poster
Session: 9-2
Location: GEO
Time: 3:30