Critical Evaluation of Kinetic Method Measurements: Possible Origins of Nonlinear Effects

• DOI: 10.1007/s13361-012-0554-0
• Publication Date: 2013-02-06T19:41:05Z
• Authors: Sandrine Bourgoin...; Carlos Afonso; Denis Lesage; Emilie-Laure Zins; Jean-Claude Tabet; P. B. Armentrout
• Keywords: Experimental data

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 are easily obtained from decompositions noncovalent heterodimers if care taken in choice method, references used, experimental conditions. Previously, several papers have focused on theoretical considerations concerning nature references. Few investigations been devoted to conditions required validate quality results. In present work, we interested rationalizing origin nonlinear effects that can be with method. It shown deviations result intrinsic properties systems investigated but also enhanced by artifacts resulting issues. Overall, it orthogonal distance regression (ODR) analysis provides optimum way acquiring accurate thermodynamic information.