Collisional Transition Probabilities for Vibrational Deactivation of Chemically Activated sec-Butyl Radicals. Diatomic and Polyatomic Molecules

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Abstract
The study of collisional transitional probabilities for the de‐excitation by inert gases of chemically activated sec‐butyl radicals, excited to internal energies in excess of 40 kcal mole−1, has been extended to H2, D2, N2, CO2, CH4, CD3F, CH3Cl, and SF6. The diatomic gases display behavior similar to the rare gases, and on a preferred exponential model of collisional transition probabilities the average amount of energy transferred per collision is 〈ΔE〉expon≃1.3 kcal mole−1. On a stepladder model the corresponding amount is ΔE≃2.5 kcal mole−1. From higher‐pressure data, the efficiency for CD3F, CH3Cl, and SF6 is deduced to be comparable with that for butene and, on a preferred stepladder model, ΔE>9 kcal. For CO2 and CH4 the behavior is intermediate. The possible importance of the role of internal rotation of butyl in facilitating energy transfer is noted; some uncertainty concerning the role of over‐all rotations and vibrational modes of the deactivator in the relaxation process exists.