The reaction of CH3O2 with ClO has been studied at 293 K using a flow reactor sampled by a mass spectrometer. Under conditions where [ClO] » [CH3O2], the CH3O2 decayed under pseudo‐first‐order conditions giving a rate coefficient of (1.9±0.4)×10−12 cm³ s−1. CH3OCl was detected as a reaction product. The implications of the measurements for the chemistry of the stratosphere are discussed briefly.
Spectroscopic and kinetic results for the quenching of [Formula: see text] are presented, including the first reported laboratory observation of gas phase emission from vibrational levels greater than zero for this state. In addition, the absolute rate constants for quenching of the lowest vibrational level by O(3P), O2(a1Δg), [Formula: see text], CO2, SF6, HE, and Ar are given. These results are compared with the results of atmospheric modeling studies. Qualitative evidence is presented for the formation of O2(a1Δg) and [Formula: see text] in the quenching of this state.
We report the observation of NH(a 1Δ) formation in a one-photon process during the ArF laser (193 nm) photolysis of ammonia. We have used laser-induced fluorescence to detect NH(a) and ND(a) and report the rotational and vibrational populations generated. We have also reinvestigated the generation of NH(a) in the 248 nm photolysis of HN3 and find substantial vibrational excitation in contrast to the results of previous workers. We give estimates for the quantum yields for NH(a) and ND(a) in the photolysis of ammonia based on comparison with the yield in 248 nm photolysis of HN3.
The fluorescence lifetime of NH(c,t,J) has been investigated for o = 0, J = 2-9 and v = 1,7= 1,4. Rate constants for quenching of NH(c,t=0) in thermal equilibrium at 298 K have been measured for 15 collision partners and for NH(c,u=0) in nonequilibrium for 8 partners. Most rate constants are near gas kinetic and decrease as the energy of the colliding pair increases. Comparison with NH(A) shows in many cases roughly a factor of 2 difference in the cross sections while there is near quantitative agreement with the cross sections for OH(A). Comparisons with the cross sections for the quenching of O/D) show a linear relationship with nonpolar and polar collision partners falling on separate parallel lines. Both the well-depth model and the complex-formation model show reasonable correlations with the data.
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