One-centre-expansion self-consistent-field (OCE-SCF) calculations on HCl. Part 3.—Electric field gradient (EFG) of the 1σ molecular orbital and the Sternheimer effect

Abstract

The interaction of the nuclear quadrupole moment with the electrons is included in the Hamiltonian of an OCE–SCF calculation on HCl. Small effects have been observed in a basis that was flexible near the Cl nucleus.

A 22-orbital OCE basis was constructed to study the polarization of the electrons in the 1st shell, the 1 σ m.o., caused by the spherical distribution of the proton and outer electrons. This polarization, the Sternheimer effect, was found to contribute 1 % to the experimental electronic EFG.

This is the first report of an SCF calculation involving direct inclusion of H^(m)_Q in the Hamiltonian.