An experimental and theoretical investigation of the competition between chemical reaction and relaxation for the reactions of ~1CH_2 with acetylene and ethene: implications for the chemistry of the giant planets

摘要

The temperature dependence of the branching ratios for H atom production from the reactions of the first excited state of methylene (a~1A_1 ~1CH_2) with acetylene and ethene have been measured at 1 Torr total pressure and temperatures of 195, 250 and 298 K by monitoring the production of H atoms using laser induced fluorescence, comparing the signal to that observed from a calibration reaction. For the reaction with acetylene the yield of H increases from 0.28 (195 K) to 0.53 (250 K) to 0.88 at 298 K. The H atom yield from the reaction of ~1CH_2 with ethene shows similar behaviour, the yields being 0.35 (195 K), 0.51 (250 K) and 0.71 (298 K). The co-products, propargyl (C_3H_3) and allyl (C_3H_5) are formed from the dissociation of chemically activated C_3H_4 and C_3H_6 intermediates respectively, and are important species in the formation of higher hydrocarbons, including benzene, in the atmospheres of the outer planets and Titan. H atom production is in competition with electronic relaxation to form ground state methylene (X~3B_1, ~3CH_2) and collisional stabilization to form C_3H_4 and C_3H_6. Master equation calculations have been carried out to demonstrate that for the reaction of ~1CH_2 with acetylene, collisional stabilization is insignificant under experimental conditions and hence the balance of reaction is due to electronic relaxation. Non-adiabatic transition state theory has been applied to the reaction of ~1CH_2 with acetylene. The calculations show reasonable agreement with experiment, generally being within the combined errors, and reproduce the negative temperature dependence for electronic relaxation. The implications of the temperature dependence of the absolute rate coefficients for ~1CH_2 reactions with inert gases, hydrogen, acetylene and ethene and of the branching ratios between chemical reaction and electronic relaxation are discussed.