The radical-radical reaction dynamics of ground-state atomic oxygen [O (P3)] with t -butyl radicals (t- C4 H9) in the gas phase were investigated using high-resolution laser spectroscopy in a crossed-beam configuration, together with ab initio theoretical calculations. The radical reactants, O (P3) and t- C4 H9, were produced by the photodissociation of N O2 and the supersonic flash pyrolysis of the precursor, azo- t -butane, respectively. A new exothermic channel, O (P3) +t- C4 H9 →OH+iso- C4 H8, was identified and the nascent rovibrational distributions of the OH (X Π2: υ″ =0,1,2) products were examined. The population analyses for the two spin-orbit states of F1 (Π 32 2) and F2 (Π 12 2) showed that the υ″ =0 level is described by a bimodal feature composed of low- and high- N″ rotational components, whereas the υ″ =1 and 2 levels exhibit unimodal distributions. No noticeable spin-orbit or Λ -doublet propensities were observed in any vibrational state. The partitioning ratio of the vibrational populations (P υ″) with respect to the low- N″ components of the υ″ =0 level was estimated to be P0: P1: P2 =1:1.17±0.24:1.40±0.11, indicating that the nascent internal distributions are highly excited. On the basis of the comparison of the experimental results with the statistical theory, the reaction mechanism at the molecular level can be described in terms of two competing dynamic pathways: the major, direct abstraction process leading to the inversion of the vibrational populations, and the minor, short-lived addition-complex process responsible for the hot rotational distributions. After considering the reaction exothermicity, the barrier height, and the number of intermediates along the addition reaction pathways on the lowest doublet potential energy surface, the formation of C H3 COC H3 (acetone) +C H3 was predicted to be dominant in the addition mechanism.
ASJC Scopus subject areas
- Atomic and Molecular Physics, and Optics