The gas-phase reaction dynamics of ground-state atomic oxygen O( 3P) from the photo-dissociation of NO2 with vinyl radicals C2H3 from the supersonic flash pyrolysis of vinyl iodide, C2H3I has been investigated using a combination of high-resolution laser-induced fluorescence spectroscopy in a crossed-beam configuration and ab initio calculations. Unlike the previous gas-phase bulk kinetic experiments by Baulch J. Phys. Chem. Ref. Data 34, 757 (2005)10.1063/1.1748524, a new exothermic channel of O(3P) C 2H3 → C2H2 OH (X 2Π: υ″ 0) has been identified for the first time, and the population analysis shows bimodal nascent rotational distributions of OH products with low- and high-N″ components with a ratio of 2.4:1. No spin-orbit propensities were observed, and the averaged ratios of Π(A ′)Π(A″) were determined to be 1.66 ± 0.27. On the basis of computations at the CBS-QB3 theory level and comparison with prior theory, the microscopic mechanisms responsible for the nascent populations can be understood in terms of two competing dynamical pathways: a direct abstraction process in the low-N″ regime as the major pathway and an addition-complex forming process in the high-N″ regime as the minor pathway. Particularly, during the bond cleavage process of the weakly bound van der Waals complex C2H2-OH, the characteristic pathway from the low dihedral-angle geometry was consistent with the observed preferential population of the Π(A′) component in the nascent OH products. A molecular-level discussion of the reactivity, mechanism, and dynamical features of the title reaction are presented together with a comparison to gas-phase oxidation reactions of a series of prototypical hydrocarbon radicals.
Bibliographical noteFunding Information:
This work was supported by a National Research Foundation of Korea Grant funded by the Korean Government (2010-0014418) and the Priority Research Centers Program through the National Research Foundation of Korea funded by the Ministry of Education, Science, and Technology (NRF20100020209).
ASJC Scopus subject areas
- General Physics and Astronomy
- Physical and Theoretical Chemistry