The v-v energy transfer of highly vibrationally excited states (II)

The vibrational energy transfer from highly vibrationally excited CO to H₂O molecules is studied by time-resolved Fourier transform infrared emission spectroscopy (TR FTIR). Following the 193 nm laser photolysis of CHBr₃ and O₂ the secondary reactions generate CO(v). The infrared emission of CO(v → v−1) is detected by TR FTIR. The excitation of H₂O molecules is not observed. By the method of the spectral simulation and the differential technique, 8 rate constants for CO(v)/H₂O system are obtained: (1.7 ±0.1), (3.4 ±0.2), (6.2 ±0.4), (8.0 ±1.0), (9.0 ±2.0), (12 ±3), (16 ±4) and (18 ±7) (10¹³cm³ · molecule^-1· s^-1). At least two reasons lead to the efficient energy transfer. One is the contributions of the rotational energy to the vibational energy defect and the other is the result of the complex collision. With the SSH andab initio calculations, the quenching mechanism of CO(v) by H₂O is suggested.