Hartree–Fock Wavefunctions and Computed Properties for the Ground (2π) States of SF and SeF and Their Positive and Negative Ions. A Comparison of the Theoretical Results with Experiment

Abstract

Self‐consistent‐field wavefunctions, near the Hartree–Fock limit, have been computed by the Roothaan expansion method for SF ( 2 π) and SeF ( 2 π) at the experimental internuclear separations. The results from the present investigation, coupled with our previous calculations on OF, show that the Hartree–Fock binding energies of OF, SF, and SeF vary nonmonotonically, in harmony with the experimental dissociationenthalpies. Other properties reported herein for SF and SeF include the vertical ionization potentials and vertical electron affinities, and the dipole and quadrupole moments for the neutral and charged species. The computed ionization potential for SF suggests that the experimental appearance potentials for SF+ are too large by approximately 2 eV. Thermodynamic calculations based on the electron affinities predict substantial stabilities for SF− and SeF− at moderate temperatures.