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

Abstract

The relaxation of the highly vibrationally excited CO (v = 1–8) by CO2 is studied by timeresolved Fourier transform infrared emission spectroscopy (TR FTIR). 193 nm laser photolysis of the mixture of CHBr3 with O2 generates the highly vibrationally excited CO(v) molecules. TR FTIR records the intense infrared emission of CO(v→v-1). The vibrational populations of each level of CO(v) have been determined by the method of spectral simulation. Based on the evolution of the time resolved populations and the differential method, 8 energy transfer rate constants of CO(v = 1–8) to CO2 molecules areobtained: (5.7±0.1), (5.9±0.1), (5.2±0.2), (3.4±0.2), (2.4±0.3), (2.2±0.4), (2.0±0.4) and (1.8±0.6) (1014 cm3 · molecule−1 · s−1), respectively. A two-channel energy transfer model can explain the feature of the quenching of CO(v) by CO2. For the lower vibrational states of CO, the vibrational energy transfers preferentially to the u3 mode of CO2 For the higher levels, the major quenching channel changes to the vibrational energy exchange between CO(v→v-1) and the u1 mode of CO2.