On the Model Dependence of Kinetic Shifts in Unimolecular Reactions:  The Dissociation of the Cations of Benzene and n-Butylbenzene

Abstract

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Dissociation kinetics of singly protonated leucine enkephalin investigated by time-resolved photodissociation tandem mass spectrometry

“…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.…”

Thermal decomposition of ethylbenzene cations (C8H10+): experiments and modeling of falloff curves

“…The rate constant k diss,∞ then can be related to specific rate constants k(E,J) of the dissociation represented here by k 2 . We have established this relationship previously [13] accounting in detail for both the E-and J-dependences of k(E,J). Using this relationship, measurements of specific and thermally averaged rate constants, k(E,J) and k diss,∞ respectively, were put on a common basis and analyzed consistently.…”

“…We have performed this full modeling in [13] using a statistical adiabatic channel model/classical trajectory (SACM/CT) approach on a short-range valence/long-range induced-dipole switching potential. Because the real potential is not available from ab initio calculations, model potentials were employed.…”

Electron attachment to POCl3. III. Measurement and kinetic modeling of branching fractions

“…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.…”