COLLISIONAL TRANSITION PROBABILITIES FOR VIBRATIONAL DEACTIVATION OF CHEMICALLY ACTIVATED SEC-BUTYL RADICALS. DIATOMIC AND POLYATOMIC MOLECULES
WASHINGTON UNIV SEATTLE
Pagination or Media Count:
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 kcalmole, was 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 1.3 kcalmole. On a step-ladder model the corresponding amount is delta E 2.5 kcalmole. 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, delta E 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 exists concerning the role of over- all rotations and vibrational modes of the deactivator in the relaxation process.
- Physical Chemistry