A superatomic molecule under the spin‐orbit coupling: Insights from the electronic properties in the thiolate‐protected Au38(SR)24 cluster

The role of the spin‐orbit coupling in Au₃₈(SR)₂₄, as a representative case for a superatomic molecules is studied to offer a complete view of the relativistic effect in heavy elements clusters. Its core can be described in as an analog to a diatomic molecule, such as F₂, allowing the electronic structure to be depicted in terms of the D_∞h point group. First, we showed the electronic structure under the spin‐orbit framework using total angular momentum representations ( j = ℓ ± s ; spinors), which allows us to characterize the expected splitting of certain levels derived from the cluster core. Accordingly, the optical properties are evaluated under spin‐orbit coupling regime, revealing differences in the low‐energy region of the absorption spectrum. Lastly, the variation of electron affinity (EA) and ionization potential (IP) properties is evaluated. This reveals characteristic consequences of the inclusion of spin‐orbit coupling in Au₃₈(SR)₂₄, as a bridge to larger thiolate‐protected gold clusters.