Systematic and random errors in ion affinities and activation entropies from the extended kinetic method

An evaluation of the extended kinetic method with full entropy analysis was conducted using RRKM theory to simulate data for collision-induced dissociation under single-collision conditions. A rigorous method for analyzing kinetic method data, orthogonal distance regression, is introduced and compared with previous methods in the literature. The results demonstrate that the use of the extended kinetic method is definitely superior to the standard kinetic method, but final ion affinities and activation entropies differ intrinsically from the correct values. Considering the effects of both systematic and random error in Monte Carlo simulations of the full entropy analysis, error distributions of +/-4 to +/-12 kJ mol(-1) for ion affinities and of +/-9 to +/-30 J mol(-1) K-1 for activation entropy differences are found (+/-2 standard deviations of the sample populations). The systematic errors in ion affinities are larger for systems with large activation entropy differences. These uncertainties do not include any error in the absolute calibration of the reference ion affinity scale. We argue that application of an empirical correction factor is inadvisable. Copyright (C) 2004 John Wiley Sons, Ltd.