Journal of Physical Chemistry A, Vol.107, No.41, 8380-8382, 2003
Evidence of a surprising channeling of ring-opening energy to the H-2 product in the H+c-C3H6 -> H-2+C3H5 abstraction reaction
The product energy disposal in the abstraction reaction H + c-C3H6 --> H-2(v', j') + C3H5 at 1.6 eV collision energy has been characterized by quantum-state-selective, Doppler-resolved REMPI detection of the H-2(v', j') product. The H-2(v', j') product is observed with total energy, translational plus rotational plus vibrational, in excess of the total available energy if the C3H5 product is a cyclopropyl radical, but the total H-2(v', j') energy matches the total available energy if the C3H5 product is allyl. This implies ring-opening of cyclopropyl to allyl concerted with abstraction and the deposition of a large fraction of the ring-opening energy into the H-2(v', j') product. Such behavior is unprecedented and entirely unexpected. Calculations indicate that both direct H-by-H abstraction and H-addition/H-2-elimination should occur too quickly to allow the isomerization to occur before product separation. Even if ring-opening did occur, the appearance of the total isomerization energy in the H-2 product would seem dynamically forbidden. The reaction must follow an unanticipated and surprising path.