Inelastic scattering from glyoxal: collision kinematics rather than the interaction potential dominates rotational channel selection.
Relative cross sections have been obtained for the rotationally and rovibrationally inelastic scattering of S1 trans-glyoxal (CHO-CHO) in its zero point level with K' = 0 from the target gases H2, D2, and He. Emphasis is placed on using crossed molecular beam conditions that provide several choices of collision kinematics (center-of-mass collision energy, relative velocity, center-of-mass collision momentum) for each collision pair. The cross sections define the state-to-state competition among numerous rotational channels involving destination states with DeltaK' ranging from 1 to >15 for collisions with each target gas and under every kinematic condition. They also resolve a similar rotational competition among rovibrational channels where the torsion nu7' is collisionally excited. The cross section sets also allow the relative overall magnitudes of the two types of scattering to be compared. The primary motivation of these experiments concerns the rotationally inelastic scattering. Earlier studies with rare gases and fixed kinematics demonstrated that the distribution of rotational cross sections is remarkably similar from one collision pair to another. The new data show that the competition among rotational channels actually has a small but distinct dependence on kinematic conditions. Data analysis shows that the dependence is a systematic function of the available collision momentum and entirely unrelated to the identity of the target gases, including the heavier rare gases used in earlier studies. The competition among the rotational energy transfer channels and its kinematic heritage is discussed in the context of a classical hard ellipse model of linear momentum to angular momentum conversion much used with room temperature systems. When adapted to our beam conditions, the resulting account of the rotational scattering is accurate and provides insight into the collisional details.
Clegg
Samuel M
SM
Department of Chemistry, Indiana University, Bloomington, Indiana 47405, USA. sclegg@lanl.gov
Parmenter
Charles S
CS