Zero virial reaction processes. Reactions of Si and Mg atoms with H2 and HF molecules

Abstract

By adopting the bond angle as a reaction coordinate and imposing on appropriate conditions, we determine a reaction path named the zero virial path starting from the reactant and arriving at the product via the transition state. At every point on this path, the polyatomic virial theorem is reduced to the simple atom-like form, and within the LCAO framework the total energy including the nuclear repulsion is partitioned exactly into the one center (atomic) and two center (bond) terms through the negative kinetic energy. Using these advantages of the zero virial path, the processes of bond formation and fission are examined in detail for the reactions of Si and Mg atoms with H2 and HF molecules.