Rotationally correlated reactivity in the CH (v=0, J, Fi) + O2 → OH (A) plus CO reaction

The rotational-state-selected CH (v = 0, J, F-i) beam has been prepared by using an electric hexapole and applied to the crossed beam reaction of CH (v = 0, J, Fi) + O-2 --> OH (A) + CO at different O-2 beam conditions. The rotational state selected reactive cross sections of CH (RSSRCS-CH) turn out to depend remarkably on the rotational state distribution of O-2 molecules at a collision energy of similar to 0.19 eV. The reactivity of CH molecules in the N = 1 rotational states (namely |J = 1/2, F-2 > and |J = 3/2, F-1 > states, N designates the angular momentum excluding spin) becomes strongly enhanced upon a lowering of the rotational temperature of the O-2 beam. The RSSRCS-CH in these two rotational states correlate linearly with the population of O-2 molecule in the specific K-O2 frame rotation number states: CH(|J = 1/2, F-2 >) with O-2(| K-O2 = 1 >); CH(|J = 3/2, F-1 >) with O-2(|K-O2 = 3 >). These linear correlations mean that the rotational-state-selected CH molecules are selectively reactive upon the incoming O-2 molecules in a specific rotational state; here, we use the term "rotationally correlated reactivity" to such specific reactivity depending on the combination of the rotational states between two molecular reactants. In addition, the steric asymmetry in the oriented CH (|J = 1/2, F-2, M = 1/2 >) + O-2 (|K-O2 = 1 >) reaction turns out to be negligible (< +/-1%). This observation supports the reaction mechanism as theoretically predicted by Huang et al. [J. Phys. Chem. A 106, 5490 (2002)] that the first step is an intermediate formation with no energy barrier in which C-atom of CH molecule attacks on one O-atom of O-2 molecule at a sideways configuration. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3560660]