Journal of Physical Chemistry p. 2253 - 2260 (1985)
Update date:2022-08-11
Topics:
Malinovich, Y.
Arakawa, R.
Haase, G.
Lifshitz, C.
Time-resolved photoionization mass spectrometry (TPIMS) in the millisecond range has been employed to study the reaction C6H5Br(1+) radical -> C6H5(1+) + Br radical in bromobenzene.Experimental photoionization efficiency curves were fitted with a QET model calculation by assuming a critical energy Eo = 2.76 eV and an activation entropy ΔS(excit.) = 8.07 eu.The activation entropy coresponds to the totally loose (orbiting) transititon state.Ultraslow unimolecular dissociations having microcanonical rate coefficients k(E) = 10 /sec, at near threshold energies, can be sampled by TPIMS, in spite of competing IR-raditive decay of the parent ion.
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