The modified Thomas-Fermi method reported in (2) has been applied numerically to calculate the distribution of valence electrons in CC14. Slater wave functions have been used to describe the Cl inner-shell electrons, whilst a description of the C ls electrons based on the Thomas-Fermi model for atoms has been adopted. The electron distribution thus found is compared with the two approximations discussed in part I of this series (3). The first of these, in which valence and inner-shell electrons are treated in the same way, is shown to give a distribution of valence electrons in good agreement with the present results. The second approximation, that of effective nuclear charges, is less satisfactory and could only lead to a distribution of valence electrons in reasonable agreement with the present work if the effective nuclear charges were considerably reduced. This seems to throw some light on the results of Bowers for the force constants of tetrachlorides and tetrabromides.

The overall distribution of electrons obtained here seems to be the inevitable result of assuming the valence electrons to move in any plausible central field. It is, of course, by no means certain that such an approximation is near to the truth. In fact, the results of (3) and the present paper leave little doubt that the electron cloud obtained by such an approximate method will be too diffuse. This seems at least partly responsible for our finding that rather more than 20 of the 28 Cl valence electrons lie outside the sphere drawn through the Cl nuclei.