TY - JOUR
T1 - Rotationally specific mode-to-mode vibrational energy transfer in D2CO/D2CO collisions. II. Kinetics and modeling
AU - Bewick, C. P.
AU - Martins, J. F.
AU - Orr, B. J.
PY - 1990/12/15
Y1 - 1990/12/15
N2 - Time-resolved infrared-ultraviolet double resonance (IRUVDR) spectroscopy is used to study the kinetics of collision-induced rovibrational energy transfer between the v6 and v4 modes of D2CO in the vapor phase. As in paper I [J. Chem. Phys. 93, 8634 (1990)] of the series, attention rests on the existence of V-V transfer channels which are rotationally specific with respect to both J and Ka. Infrared excitation by the 10R (32) CO2-laser line prepares D2CO in two discrete rovibrational states, (J,Ka,Kc) = (11,4,7) and (7,2,6), of the v6 = 1 vibrational manifold. D2CO/D2CO collisions then disperse this selected population to various states of the (v4,v6) rovibrational manifold, through a combination of rotational energy transfer (RET) and v6 → v4 transfer. This yields an extensive range of (J,Ka)-resolved IRUVDR kinetic curves, demonstrating the collision-induced evolution of rovibrational population and enabling that evolution to be modeled by means of a master-equation approach. The features of the model of best fit are as follows: the dominant K a-resolved channel of v6→ v4 transfer is that with Ka= 4→6; accompanying J-resolved v6- →v4 transfer channels favor ΔJ = 0, with state-to-state rate constants scaling as J3.4; additional (J,Ka)-resolved v6→v4 channels allow a spread of J- and K a-changing V-V transfer. These features are consistent with the accepted mechanism of v6-→v4 transfer in D 2CO, involving enhancement by a combination of Coriolis coupling and rotor asymmetry perturbations. In addition to v6→v4 transfer, RET provides the predominant channels of collision-induced relaxation: J-changing RET is described by a conventional fitting law based on the energy gap |ΔE| for the state-selected molecule; Ka-changing RET favors even values of ΔKa and, contrary to previous expectations, is J selective with a propensity for ΔJ = 0. The physical implications of these results are discussed.
AB - Time-resolved infrared-ultraviolet double resonance (IRUVDR) spectroscopy is used to study the kinetics of collision-induced rovibrational energy transfer between the v6 and v4 modes of D2CO in the vapor phase. As in paper I [J. Chem. Phys. 93, 8634 (1990)] of the series, attention rests on the existence of V-V transfer channels which are rotationally specific with respect to both J and Ka. Infrared excitation by the 10R (32) CO2-laser line prepares D2CO in two discrete rovibrational states, (J,Ka,Kc) = (11,4,7) and (7,2,6), of the v6 = 1 vibrational manifold. D2CO/D2CO collisions then disperse this selected population to various states of the (v4,v6) rovibrational manifold, through a combination of rotational energy transfer (RET) and v6 → v4 transfer. This yields an extensive range of (J,Ka)-resolved IRUVDR kinetic curves, demonstrating the collision-induced evolution of rovibrational population and enabling that evolution to be modeled by means of a master-equation approach. The features of the model of best fit are as follows: the dominant K a-resolved channel of v6→ v4 transfer is that with Ka= 4→6; accompanying J-resolved v6- →v4 transfer channels favor ΔJ = 0, with state-to-state rate constants scaling as J3.4; additional (J,Ka)-resolved v6→v4 channels allow a spread of J- and K a-changing V-V transfer. These features are consistent with the accepted mechanism of v6-→v4 transfer in D 2CO, involving enhancement by a combination of Coriolis coupling and rotor asymmetry perturbations. In addition to v6→v4 transfer, RET provides the predominant channels of collision-induced relaxation: J-changing RET is described by a conventional fitting law based on the energy gap |ΔE| for the state-selected molecule; Ka-changing RET favors even values of ΔKa and, contrary to previous expectations, is J selective with a propensity for ΔJ = 0. The physical implications of these results are discussed.
UR - http://www.scopus.com/inward/record.url?scp=0040224727&partnerID=8YFLogxK
U2 - 10.1063/1.459251
DO - 10.1063/1.459251
M3 - Article
AN - SCOPUS:0040224727
SN - 0021-9606
VL - 93
SP - 8643
EP - 8657
JO - The Journal of Chemical Physics
JF - The Journal of Chemical Physics
IS - 12
ER -