The structure of molecular effective potentials in compounds of heavy elements, with application to I2

Abstract

A new expression of the Phillips–Kleinman pseudopotential for many‐valence‐electron molecules is proposed. All remaining terms in the valence Hamiltonian, represented by a local potential, are evaluated from ab initio expressions based on the form of the atomic Fock operator. Sample calculations are reported for the orbital energies, equilibrium bond length, and vibrational frequency of the ground state of the I₂ molecule.