Thermochemical spin‐orbit corrections for atomic platinum (Pt)

Abstract

AbstractIn quantum chemistry calculations of molecular dissociation or atomization, the energies of many atoms require spin‐orbit corrections (SOCs). This is to compensate for the lack of spin‐orbit coupling in most calculations. Values for the corrections are normally derived from experimental atomic energy levels and their assignments to LS (Russell‐Saunders) terms. However, this procedure produces erroneous values when terms are strongly mixed, as they are in Pt. Spin‐orbit configuration interaction provides the LS‐term composition of observed energy levels. Such data are used here to obtain SOCs for valence term energies of Pt. For the ground term (3D), a correction of −3948 ± 153 cm−1 is recommended.