Ab initio calculations, using a small Gaussian basis set, of the electronic structure of the sulphate ion

Ab initio molecular orbital calculations of the electronic structure of the sulphate ion have been performed in which three Gaussian‐type functions are used to simulate each member of a minimal basis of Slater‐type orbitals. Comparative calculations on H 2 S show that such a basis excellently reproduces the properties of the valence electrons given by calculations in a Slater basis. The expansion of the basis by the addition of sulphur 3 d orbitals results in a large decrease in the molecular energy (1 a.u.) and has a pronounced effect on the ordering and energy of the molecular orbitals. The results of a number of semiempirical schemes are discussed in the light of these results.