Structural Considerations in Chemical Kinetics: Gas Phase H‐Atom Transfer Reaction Series

Structure–reactivity correlations are discussed and applied to the X + H₂ → XH + H and Cl + HX → ClH + X series of gas phase reactions where X is a halogen atom. In particular, potential energy surfaces for the (collinear) XH₂ system are obtained in terms of the diatomic, H₂ and XH, potentials and two parameters which are common to all members of the series. These surfaces are in quantitative accord with the Evans–Polanyi, Leffler and Hammond postulates. The rate constants satisfy the reactivity‐selectivity principle.