ABINITIO COUPLED HARTREE-FOCK CALCULATION OF THE NUCLEAR SHIELDING IN THE H2-HE INTERACTING SYSTEM

A coupled Hartree—Fock scheme has been used to calculate the elements of the nuclear shielding tensors in the H2/He interacting system. The effects of the basis set size and the choice of origin for the magnetic vector potential have been examined. The results of the calculation lead to several estimates of the repulsive contribution to the N.M.R. shielding virial coefficient oH, Ee, the best one of which is + 3 ppm cm3 mol-1. Although an experimental value of the virial coefficient is unavailable for the H2/He system, results for other mixtures have the same order of magnitude but an opposite sign. This suggests in general that, though attractive contributions are predominant in affecting the shielding changes due to intermolecular interaction, the repulsive contributions are by no means negligible as has sometimes been assumed. © 1979 Taylor & Francis Group, LLC.