Molecules With tetrahedral and octahedral symmetry. IV. A modified Thomas–Fermi scheme for molecules with heavy atoms in the outer positions

Abstract

ABSTRACTIn Part I of this series it was shown that for CCl4 the approximation of smoothing out the Cl nuclei over the surface of a sphere did not lead to reasonable results for the Thomas–Fermi distribution of electrons in the molecule. An alternative method in which the inner-shell Cl electrons were first compressed into the nuclei was not theoretically satisfactory because of the neglect of the exclusion principle. In this paper therefore a general scheme is presented in which we describe the inner-shell electrons of the outer atoms wave mechanically, assuming them to be undisturbed by molecular binding, but still use a Thomas–Fermi description for the valence electrons. A method by means of which the exclusion principle can be imposed is formulated. The following paper of the series deals with the application of the method described here to obtain an improved valence electron distribution in CCl4.