Ground states of molecules. 56. <scp>MNDO</scp> calculations for molecules containing sulfur

Abstract

Abstract MNDO has been extended to sulfur, but without inclusion of 3 d AO s. Calculations are reported for heats of formation, geometries, dipole moments, and ionization energies of a variety of sulfur‐containing molecules. The average discrepancy between calculated and observed heats of formation is larger than for compounds of other elements, a difference probably due, at least partly, to the lower accuracy of the thermochemical data for sulfur compounds. The calculated dipole moments agree well with experiment as do the calculated ionization energies, except for those corresponding to ionization from sulfur “lone‐pair” orbitals which are too high by ca. 1 eV, probably as a result of the neglect in NDDO of interactions between inner and valence shell orbitals. As in the case of other third‐period elements, the calculated heats of formation of compounds of sulfur in its higher valence states (S IV , S VI ) were too positive by large amounts, due presumably to the neglect of 3 d AO s.