Time-Dependent Mass Spectra and Breakdown Graphs. 8. Dissociative Photoionization of Phenol

Article abstract of DOI:10.1021/j100409a018

Time-resolved photoionization mass spectrometry in the millisecond range has been employed to study the reaction C6H5OH<*>(1+) --> cC5H6<*>(1+) + CO in phenol.Experimental photoionization efficiency 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.The experimental breakdown curves for 2 ms are the first to be obtained by photoionization for such a long reaction time in any system.A sensitivity analysis yielded the following activation parameters: critical energy of activation, E₀ = 67.6+/-0.9 kcal/mol, and entropy of activation, ΔS<*> (1000 deg K) = 2.2+/-1.2 eu.