2008 **Abstract:** Specific rate constants k(E) of the dissociation of the halobenzene ions C6H5X+ --> C6H5+ + X* (X* = Cl, Br, and I) were measured over a range of 10(3)-10(7) s-1 by threshold photoelectron-photoion coincidence (TPEPICO) spectroscopy. The experimental data were analyzed by various statistical unimolecular rate theories in order to derive the threshold energies E0. Although rigid activated complex RRKM theory fits the data in the experimentally measured energy range, it significantly underestimates E0 for chloro…

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“…Autodetachment (8) and dissociation (10) specific rate curves are calculated using statistical theory by employing microscopic reversibility 43 of (7) and by employing the simplified statistical adiabatic channel model. 44,45 Finally, competition between (8)- (10) is determined by explicitly accounting for collisions with the buffer gas and approximating the solution to the Master Equation using the many-shots approach. 13,46 As determined with the kinetic modeling, neither stabilization of C 2 F − * 5 through collisions with the buffer gas, process (9), nor autodetachment (8) occur quickly enough to compete with the dissociation, process (10).…”

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“…Autodetachment (8) and dissociation (10) specific rate curves are calculated using statistical theory by employing microscopic reversibility 43 of (7) and by employing the simplified statistical adiabatic channel model. 44,45 Finally, competition between (8)- (10) is determined by explicitly accounting for collisions with the buffer gas and approximating the solution to the Master Equation using the many-shots approach. 13,46 As determined with the kinetic modeling, neither stabilization of C 2 F − * 5 through collisions with the buffer gas, process (9), nor autodetachment (8) occur quickly enough to compete with the dissociation, process (10).…”

“…Also, based on the previous study [25] on [Y 6 ϩ H] ϩ using three instruments with different ion-optical layouts, we are confident that the instrumental factors such as mass discrimination are well taken care of. For reactions occurring via loose transition-state, it is known [32,33] that RRKM fitting of experimental data tends to result in dissociation energies that are a little smaller (by 6% or less) than correct values. Such errors might be unimportant for the present reactions occurring via tight transition states.…”

“…Like in Ref. 3, we employ a statistical adiabatic channel model/classical trajectory (SACM/CT) approach [20][21][22][23][24][25] for the characterization of k diss (E). We express k diss (E) by 6) where k(E) PST is obtained from phase space theory (PST) and the total rigidity factor f tot rigid (E), being smaller than unity, accounts for the anisotropy of the potential.…”

“…The functional form of f tot rigid (E) is not obvious. Since publishing part I, in an analysis of halobenzene cation dissociations 24 we have gained more experience with simplified one-fit parameter expressions to determine…”