title: Theoretical determinations of the ambient conformational distribution and unimolecular decomposition of n-propylperoxy radical.
abstract: The conformational distribution and unimolecular decomposition pathways for the n-propylperoxy radical have been generated at the CBS-QB3, B3LYP/6-31+G and mPW1K/6-31+G levels of theory. At each of the theoretical levels, the 298 K Boltzmann distributions and rotational profiles indicate that all five unique rotamers of the n-propylperoxy radical can be expected to be present in significant concentrations at thermal equilibrium. At the CBS-QB3 level, the 298 K distribution of rotamers is predicted to be 28.1, 26.4, 19.6, 14.0, and 11.9% for the gG, tG, gT, gG', and tT conformations, respectively. The CBS-QB3 C-OO bond dissociation energy (DeltaH298 K) for the n-propylperoxy radical has been calculated to be 36.1 kcal/mol. The detailed CBS-QB3 potential energy surface for the unimolecular decomposition of the n-propylperoxy radical indicates that important bimolecular products could be derived from two 1,4-H transfer mechanisms available at T < 500 K, primarily via an activated n-propylperoxy adduct.
authors.affiliation: Department of Chemistry, The Ohio State University, 100 West 18th Avenue, Columbus, Ohio 43210, USA.
authors.forename: John K
authors.initials: JK
authors.lastname: Merle
authors.forename: Carrigan J
authors.initials: CJ
authors.lastname: Hayes
authors.forename: Sergey J
authors.initials: SJ
authors.lastname: Zalyubovsky
authors.forename: Brent G
authors.initials: BG
authors.lastname: Glover
authors.forename: Terry A
authors.initials: TA
authors.lastname: Miller
authors.forename: Christopher M
authors.initials: CM
authors.lastname: Hadad