Collisional effects on angular momentum orientation in acetylene (X)over-tilde (1)Sigma(+)(g) (nu(2)''=1, j ''). I. Preparation, detection and conservation in single collisions
Ad. Rudert et al., Collisional effects on angular momentum orientation in acetylene (X)over-tilde (1)Sigma(+)(g) (nu(2)''=1, j ''). I. Preparation, detection and conservation in single collisions, J CHEM PHYS, 111(21), 1999, pp. 9549-9559
The effect of rotationally inelastic collisions on the orientation of the a
ngular momentum is investigated for C2H2 (nu(2) = 1, j). The orientation of
the angular momentum in initial rotational states j(i) = 7 to 13 is prepar
ed by stimulated Raman pumping using circularly polarized light and S-branc
h transitions. After allowing an appropriate time for collisions to occur t
he orientation is probed by laser-induced fluorescence in the (A) over tild
e (1)A(u)<--(X) over tilde (1)Sigma(g) transition. For acetylene the theore
tically calculated and the measured initial orientation, A(0)((1)), ranges
between 0.7 and 0.9. A substantial part of the orientation is conserved in
rotationally inelastic collisions, which could be measured up to \Delta j\
= 6 with sufficient signal-to-noise ratio. These results are compared with
previous measurements on the conservation of alignment in collisions. Rotat
ionally inelastic collisions with \Delta j\ = 2 result in an average rotati
on of the orientation vector by about 30 degrees. The amount of orientation
that remains after a rotationally inelastic collision is found to depend p
rimarily on \Delta j\. A Delta m(j) = 0 propensity rule often used in model
s of rotational energy transfer is found to be inconsistent with the measur
ements. Also a model which proposes a minimum change of the classical angle
phi between j and the quantization axis does not reproduce well the experi
mental data. Finally, a microscopic model for Delta m(j)-transitions is pre
sented which reconciles both alignment and orientation measurements. (C) 19
99 American Institute of Physics. [S0021-9606(99)01445-2].