Journal of Chemical Physics, Vol.101, No.9, 7468-7479, 1994
On the Generation of Preferential Lambda-Doublet Populations in the Collisional Relaxation of Highly Rotationally Excited CH(X(2)Pi)
By means of full quantum close-coupling and coupled states calculations based on an ab initio potential energy surface for the Ar-CH system, we confirm a propensity seen experimentally by Hancock, Stuhl, and their co-workers. During the rotational relaxation of high rotational levels of the CH(X (2) Pi) radical, produced by photolysis of a suitable precursor, there appears a clear population imbalance in favor of the Lambda-doublet levels of Pi(A") symmetry. A full kinetic simulation, based on the calculated cross sections, reproduces nearly quantitatively the experimental observations of both the temporal evolution and the pressure dependence of this h-doublet asymmetry. This asymmetry is a consequence of both an enhanced depletion of high N Pi(A’) levels and the enhanced formation of Pi(A") levels in the next lower (N-1) manifolds. The physical origin of this propensity involves a crossing between two adiabatic bender potentials which follow, respectively, the A’ and A" potential energy surface (PES). This crossing occurs only for the "helicopter-like" approach of the CH molecule, in which its rotational angular momentum is aligned along the initial relative velocity vector. Thus, a strong upsilon, N correlation in the reactant channel results in a strong Lambda, N correlation in the product channel.
Keywords:INTEGRAL CROSS-SECTIONS;CLOSE-COUPLING APPROACH;PI-ELECTRONIC STATES;INELASTIC-COLLISIONS;VANDERWAALS COMPLEXES;STRUCTURE TRANSITIONS;DIATOMIC MOLECULE;LINEAR-MOLECULES;ENERGY-TRANSFER;FINE-STRUCTURE