화학공학소재연구정보센터
Journal of Chemical Physics, Vol.101, No.9, 7440-7450, 1994
Crossed-Beam Rovibrational Energy-Transfer from S-1 Glyoxal .4. Reduced Mass Effects and an Overview of the Inelastic-Scattering Characteristics from 4 Initial Levels
Crossed molecular beam studies of rotationally and rovibrationally inelastic scattering of S-1 glyoxal from H-2 and He have been extended to one additional light gas, D-2, and to two heavy gases of identical masses, Kr and cyclohexane, C6H12 (84 amu). Laser excitation was used to prepare glyoxal in its 0(0) level with K’=0 and 0 less than or equal to J’less than or equal to 10, Dispersed fluorescence detection was used to observe the final K’ and vibrational states of the inelastic scattering. The relative scattering cross sections for D-2 and He collisions are identical to within experimental error and differ substantially from those of H-2. The Kr and C6H12 cross sections are also a matched set. These results show that the competition among the approximately 25 observable scattering channels is far more sensitive to the reduced mass of the collision than to variation in the intermolecular potential or even the internal structure of the target gas. An overview of rotational and rovibrational scattering in glyoxal from four vibrational levels (0(0), 7(2), 5(1), and 8(1)) extending to epsilon(vib)=735 cm(-1) is used to uncover generalities and insights about the energy transfer. For all four initial levels the vibrational state changes are highly selective. The detectable channels are always limited to +/-1 quantum change in only one of the 12 modes, specifically nu(7)’ = 233 cm(1), the lowest frequency mode. The cross sections for vibrational state change are surprisingly large relative to those for pure rotationally inelastic scattering. Many cases occur with the light target gases where the Delta K resolved cross sections for rovibrational interactions are nearly equal to those for pure rotationally inelastic scattering with equivalent energy transfer Delta E. Scattering from 7(2), K’=0 glyoxal contains examples with both H-2 and He where the rovibrational cross sections actually exceed those for rotational scattering. Plots of the entire set of cross sections [rotational (Delta K) plus rovibrational (Delta upsilon(7) = +1)] against Delta E are essentially superimposible for He scattering from 0(0), 5(1), and 8(1) glyoxal. In contrast, scattering from 7(2) glyoxal with the active mode initially excited is distinctive. For all initial levels, the distribution of cross sections for different Delta K within rotational channels differs from that within rovibrational channels. It is further seen in these comparisons that the change in angular momentum Delta K rather than Delta E controls the relative sizes of cross sections within these channels. The theoretical predictions of Clary, Kroes, and Rettschnick are in accord with these trends and distinctions, agreeing even on some rather subtle points.