Coupled Hartree–Fock and finite perturbation–configuration interaction calculations of nuclear spin–spin coupling constants in the second-row hydrides

Abstract

Nonempirical calculations are reported for the one‐bond and geminal nuclear spin–spin coupling constants in the hydrides of the second‐row elements, HCl, H2S, PH3, and SiH4. For the Fermi contact term, the calculations are performed using the finite perturbation method at the Hartree–Fock and configuration interaction levels of approximation. The correlation effects are found to be of importance. The noncontact terms are calculated using the infinitesimal coupled Hartree–Fock method. These terms are sizable for the one‐bond couplings in HCl and H2S but small in other cases. In general, the trends in the calculated values are found to differ substantially from the situation in the first‐row hydrides, in agreement with the experimental evidence. The calculated values agree quite well with the available experimental data.