Abstract
Theories of barrier height control in radical−molecule reactions must be tested against data spanning a wide range in reactivity, by a method for separating multiple, correlated terms in the theories. Here we present an analysis technique designed to reveal reactant properties controlling reactivity and rate constant measurements for an extensive series of reactions where that control is very much in doubt. The measurements were made with a new high-pressure flow experiment designed specifically to facilitate the study of multiple radicals. The derivative technique consists of graphically analyzing partial derivatives of modeled barrier heights, using measured barriers and reactant properties. We use this technique to uncover the governing parameters for hydrogen atom abstraction reactions, which are dominated by an essentially ionic excited state of the reactants. More generally, multiple excited states contribute to barrier formation, with different states dominating for different classes of reactions. ...
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