Orbital symmetry, orbital stability, and orbital pairing rules for organic reactions in the ground state

Abstract

AbstractA generalization of the Hartree–Fock molecular orbital (MO) theory for treating diradical intermediates was explained pictorially by drawing molecular orbitals of diradical species such as ring‐opened trimethylene. The generalized MO theory applied to elucidate electronic mechanisms of concerted, ionic, radical, and ion‐radical reactions of organic reactants in the ground state. Generalized MO computations revealed the most essential characteristics of these reactions and mutal relationships between the worlds of Woodward–Hoffmann and Hughes–Ingold. Generalized MO studies supported our orbital symmetry, stability and pairing rules for concerted, ionic and radical reactions in the ground state, respectively. An extension of MO treatments to excited states reactions was briefly pointed out in relation to the density and spin correlation functions by the multireference CI wave functions.