Molecular-orbital theory of organometallic compounds. Part VIII. A comparison of the 4d and 5d radial wave functions of the second and third transition series

Abstract

A comparison is made of the various radial wave functions for the 4d and 5d atomic orbitals of the second and third transition series. Selected outer and inner properties such as Slater–Condon integrals and cusp values are compared. It is concluded from comparisons of the overlap integrals S(2p_σnd_σ) and S(2p_πnd_π) between the metal nd orbital and carbon 2p orbital, that it is most advisable in calculations on organometallic complexes of these elements to employ the new analytic functions of Basch and Gray. Previous qualitative discussions in terms of Slater functions are likely to be incorrect even in the prediction of trends.