Angular momentum conservation in multichannel unimolecular reactions

✍ Scribed by Sean C. Smith; Robert G. Gilbert

• Publisher: John Wiley and Sons
• Year: 1988
• Tongue: English
• Weight: 651 KB
• Volume: 20
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/kin.550201206

✦ Synopsis

A recently developed solution of the master equation for unimolecular and recombination reactions is extended to give new means for incorporating angular momentum ( J ) conservation in the fall-off regime for multichannel reactions. The calculated pressure dependence of a typical multichannel unimolecular dissociation reaction (thermal dissociation of 1-iodopropane) shows that if one of the channels has a transition state with a moment of inertia (1') significantly different from that of the parent molecule (I) (e.g., a "simple-fission" type), neglect of angular momentum conservation causes the predicted branching ratio to be grossly in error at lower pressures. Specifically, if 1-> I the rate coefficient is underestimated whereas if It < I the rate coefficient is overestimated.