title: Hydrogen transfer reaction in polycyclic aromatic hydrocarbon radicals.
abstract: Density functional theory calculations have been successfully applied to investigate the formation of hydrocarbon radicals and hydrogen transfer pathways related to the chemical vapor infiltration process based on model molecules of phenanthrene, anthra[2,1,9,8-opqra]tetracene, dibenzo[a,ghi]perylene, benzo[uv]naphtho[2,1,8,7-defg]pentaphene, and dibenzo[bc,ef]ovalene. The hydrogen transfer reaction rate constants are calculated within the framework of the Rice-Ramsperger-Kassel-Marcus theory and the transition state theory by use of the density functional theory calculation results as input. From these calculations, it is concluded that the hydrogen transfer reaction between two bay sites can happen almost spontaneously with energy barrier as low as about 4.0 kcal mol(-1), and the hydrogen transfer reactions between two armchair sites possess lower energy barrier than those between two zigzag sites.
authors.affiliation: Department of Chemistry, Innovative Drug Research Center, College of Sciences ‡ Research Center for Composite Materials Shanghai University , 99 Shangda Road, Shanghai 200444, China.
authors.forename: Huiting
authors.initials: H
authors.lastname: Liu
authors.forename: Liuming
authors.initials: L
authors.lastname: Yan
authors.forename: Baohua
authors.initials: B
authors.lastname: Yue
authors.forename: Aijun
authors.initials: A
authors.lastname: Li
mesh_terms: D006859:Hydrogen / Q000737:chemistry*; D007700:Kinetics; D008958:Models, Molecular; D015394:Molecular Structure; D011084:Polycyclic Aromatic Hydrocarbons / Q000737:chemistry*; D011789:Quantum Theory; D013816:Thermodynamics
chemical_list: D011084:Polycyclic Aromatic Hydrocarbons; D006859:Hydrogen