Journal of Chemical Physics, Vol.101, No.9, 7423-7439, 1994
Crossed-Beam Rovibrational Energy-Transfer from S-1 Glyoxal .3. Quantitative H-2 and He Cross-Sections for (0(0), K’=0) and (7(2), K’=0) and Comparison with Theory
Results of crossed-molecular beam inelastic scattering experiments from two levels of (1)A(u) (S-1) trans-glyoxal in collisions with H-2 (E(c.m.)=80 meV, 650 cm(-1)) and He (E(c.m.)=95 meV, 770 cm(-1)) are reported. Relative inelastic scattering cross sections with quantitative error bars are obtained. S-1>--S-0 laser excitation was used to prepare either the 0(0) level or the 7(2) level (epsilon(vib)=466 cm(-1)) with the high rotational selection of K’=0 and J’=0-10. The final high levels populated by rotationally and rovibrationally inelastic scattering were monitored by dispersed fluorescence with K’ state resolution. Fluorescence from only those molecules involved in inelastic scattering was obtained from the difference signal of spectra with the target gas beam (H, or He) ON and OFE Those dispersed fluorescence spectra were analyzed with a computer fitting procedure to extract 52 relative state-to-state cross sections for scattering from the (0(0), K’=O) level and 84 for the (7(2), K’=O) level. The cross sections have been compared quantitatively with the results of the three-dimensional quantal scattering calculations of Clary, Dateo, Kroes, and Rettschnick. The agreement between the experimental and theoretical cross sections is nearly quantitative for both target gases and both initial states. Disagreements between experiment and theory occur only in the details of K’ distributions within the rovibrational channels. The vibrationally inelastic scattering is extremely selective among the many accessible channels. The cross sections for Delta upsilon(1)=+/-1 changes in the lowest frequency mode upsilon’(7)= 233 cm(-1), a CKO-CHO torsion, exceed those involving the other 11 modes by at least an order of magnitude. As judged by the relative magnitudes of rovibrational and rotational cross sections, rovibrational scattering is surprisingly efficient. In fact, when comparing cross sections for transferring energy by (T-->R) vs (T-->R,V) with similar Delta E, rovibrational cross sections are the greater in numerous examples.