M. Kind et al., Fine-structure state resolved rotationally inelastic collisions of CH(A (2)Delta,v=0) with Ar: A combined experimental and theoretical study, J CHEM PHYS, 114(10), 2001, pp. 4479-4489
A collaborative experimental and theoretical study of rotationally inelasti
c collisions of CH(A (2)Delta,upsilon = 0) resolved rotational/fine-structu
re levels with argon is presented. Experimental state-to-state rate constan
ts were extracted from CH A (2)Delta --> X (2)Pi fluorescence spectra upon
laser excitation to individual levels in the A (2)Delta state in the presen
ce of Ar. Fluorescence detection of the collision-induced population permit
s resolution of the fine-structure levels at low N, but no Lambda -doublet
discrimination. For the lowest value of N (N = 2), the dominant process is
the DeltaN = 0 fine-structure-changing transition, and the efficiency of th
is transition decreases markedly with increasing N. There is an increasing
preference for conservation of the fine-structure label in DeltaN not equal
0 transitions as N increases. These rate constants have been compared to a
nd interpreted with theoretical rate constants computed through quantum cou
pled-states calculations of cross sections based on ab initio CH(A (2)Delta
)-Ar potential energy surfaces determined by Kaledin and Heaven (to be publ
ished). The tendency to conserve the fine-structure label is attributed to
the Hund's case (b) nature of the CH(A (2)Delta) state, for which the elect
ron spin is a spectator in the collision. (C) 2001 American Institute of Ph
ysics.