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Critical Evaluation of Kinetic Method Measurements: Possible Origins of Nonlinear Effects |
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| Authors: | Sandrine Bourgoin-Voillard Carlos Afonso Denis Lesage Emilie-Laure Zins Jean-Claude Tabet P B Armentrout | |
| Institution: | 1. Institut Parisien de Chimie Moléculaire, UMR CNRS 7201, Université Pierre et Marie Curie-Paris6, Paris, France 5. Cibles diagnostiques ou thérapeutiques et vectorisation de drogues dans le cancer du poumon INSERM U823, Institut Albert Bonniot, Université Joseph Fourier Plate-forme de Protéomique Promethée, Institut de Biologie et Pathologie, CHU de Grenoble BP217, 38043, Grenoble Cedex 9, France 2. UMR CNRS 6014 COBRA, Université de Rouen, INSA de Rouen, Mont-Saint-Aignan, France 3. Laboratoire de Dynamique, Interactions et Réactivité, LADIR, UMR 7075, CNRS, Université Pierre et Marie Curie-Paris6, Paris, France 4. Department of Chemistry, University of Utah, Salt Lake City, UT, 84112, USA |
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| Abstract: | The kinetic method is a widely used approach for the determination of thermochemical data such as proton affinities (PA) and gas-phase acidities (ΔH° acid ). These data are easily obtained from decompositions of noncovalent heterodimers if care is taken in the choice of the method, references used, and experimental conditions. Previously, several papers have focused on theoretical considerations concerning the nature of the references. Few investigations have been devoted to conditions required to validate the quality of the experimental results. In the present work, we are interested in rationalizing the origin of nonlinear effects that can be obtained with the kinetic method. It is shown that such deviations result from intrinsic properties of the systems investigated but can also be enhanced by artifacts resulting from experimental issues. Overall, it is shown that orthogonal distance regression (ODR) analysis of kinetic method data provides the optimum way of acquiring accurate thermodynamic information.  | |
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