Abstract
Time-resolved photoionization mass spectrometry in the millisecond range has been employed to study the reaction C 6H 5OCH + 3 → C 6H + 6 + CH 2O in anisole. Photoionization efficiency (PIE) curves gave a long-time limiting appearance energy value, AE = 10.85 ± 0.05 eV at 298 K. Experimental PIE curves and breakdown graphs at t = 6 μs and 2 ms were compared to those predicted by the statistical theory (RRKM/QET) and by previous photoelectron—photoion coincidence spectrometry results. A sensitivity analysis yielded the following activation parameters: critical energy of activation, E 0 = 59.6 ± 0.6 kcal/mol, and entropy of activation, Δ S ‡(1000 K) = 7.25 ± 2.2 eu.
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