title: Observation of transition-state vibrational thresholds in the rate of dissociation of ketene.
abstract: Rate constants for the dissociation of highly vibrationally excited ketene (CH(2)CO) have been measured at the threshold for the production of CH(2)((3)B(1)) and CO((1)Sigma(+)). The rate constant increases in a stepwise manner with increasing energy, consistent with the long-standing premise that the rate of a unimolecular reaction is controlled by flux through quantized transition-state thresholds. The data give the energies of the torsional and C-C-O bending vibrations of the transition state.
authors.forename: E R
authors.initials: ER
authors.lastname: Lovejoy
authors.forename: S K
authors.initials: SK
authors.lastname: Kim
authors.forename: C B
authors.initials: CB
authors.lastname: Moore