title: Matrix infrared spectra and density functional calculations of the H2CCN and H2CNC radicals produced from CH3CN.
abstract: The H(2)CCN and H(2)CNC radicals are observed in matrix IR spectra from acetonitrile exposed to radiation from laser ablation of transition metals, whereas cyc-H(2)CCN, another plausible isomer, is not. Density functional frequency calculations and D and (13)C isotopic substitutions substantiate the vibrational assignments. The cyano methyl radical converts to the 95 kJ/mol higher energy isocyano counterpart on uv photolysis. Computations show that the cyclic isomer is a shallow energy minimum between two transition states. Intrinsic reaction coordinate calculations indicate that conversion between the two products is feasible via the cyclic configuration.
authors: Department of Chemistry, University of Incheon, 119 Academy-ro, Songdo-dong, Yonsu-gu, Incheon, 406-772, South Korea.
authors: Han-Gook
authors: HG
authors: Cho
authors: Lester
authors: L
authors: Andrews