Abstract
The method of arrested relaxation has been applied to the study of infrared chemiluminescence arising from HClv′>0 formed in the reaction H + SCl2 → HCl + SCl. The main findings are (a) that the mean fraction of the available energy entering vibration in the new bond is similar to that for the reaction H + Cl2 → HCl + Cl, the value being ≈ 0.43 (assuming the energy available for distribution among the products to be ); (b) that the breadth of the distribution over the populated vibrational levels, v′ = 1–5, substantially exceeds that for H + Cl2 → HCl + Cl, indicating altered reaction dynamics; (c) that the rotational distribution in the newly formed HCl is double-peaked, suggesting two distinct types of reaction dynamics (neither closely resembling that for H + Cl2), one of which gives rise to HCl with modest rotational excitation and one to HCl with a high degree of rotational excitation; (d) the mean fraction of entering product rotation (averaged over all reactive encounters) is ≈ 0.19; (e) the group of reactive encounters that result in less rotationally excited HCl are distinguished from the group that result in highly rotationally excited HCl, by differing correlation with v′ this is further evidence that two distinct types of dynamics are involved in the reaction H + SCl2 − HCl + SCl.
© 1971 Optical Society of America
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