On the dynamics of free-radical disproportionation reactions

1432-2234

Disproportionation ; Recombination ; Unimolecular reactions ; Trajectory calculations

Springer Online Journal Archives 1860-2000

Chemistry and Pharmacology

Summary Usingab initio potential surfaces, classical (co-planar) trajectory calculations were made for the combination of H+BeH and of CH+CH. For the former reaction, disproportionation to H2+Be was rare, occurring only for a linear H...H...Be configuration. Likewise, in the second case, the formation of CH2+C occurs only via a direct reaction. The principal mechanism in the CH+CH reaction is to form [C2H2]*, which dissociates into C2H + H, or very occasionally, directly into C2+H2. If the energy is very high, the C2H radical can dissociate into C2+H, but sometimes [C2H2]* itself may dissociate simultaneously into C2+H+H.

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