The relativistic theory of chemical binding

Abstract

Starting from Breit's relativistic equation for a system of two electrons, it is shown that for a hydrogen molecule (or for a system of two electrons moving in a field of cylindrical symmetry) the component of the total angular momentum (J _x) along the axis of the molecule (axis of symmetry) is a constant of motion. Thus every eigenstate of the system is simultaneously an eigenstate of J _x also, and a state of the system will specify, besides its energy, only the eigenvalue of the component of the angular momentum parallel to the axis of symmetry. The form of the four large components of the wave function relating to their dependence on the azimuthal co-ordinates has been given. The case of Russel-Saunders approximation has been considered in detail and the nature of the components of the wave function for the singlet and triplet states has been discussed. It is shown that the wave function for the ground state of the hydrogen molecule could be expressed as a sum of a set of symmetric functions of which the first term is the Heitler-London function, and that the wave function for a triplet state should be a superposition of anti-symmetric molecular orbitals. It is shown that relativistic theory brings about in a natural manner the facts relating to the ground state of the molecules C₂ and O₂. Finally, some remarks are made concerning the case of molecules for which the spinorbit and the spin-spin couplings are strong.