New insight into the electronic shell of Au38(SR)24: a superatomic molecule

Abstract

Based on the recently proposed super valence bond model, in which superatoms can compose superatomic molecules by sharing valence pairs and nuclei for shell closure, the 23c-14e bi-icosahedral Au₂₃⁽⁺⁹⁾ core of Au₃₈(SR)₂₄ is proved to be a superatomic molecule. Molecular orbital analysis reveals that the Au₂₃⁽⁺⁹⁾ core is an exact analogue of the F₂ molecule in electronic configuration. Chemical bonding analysis by the adaptive natural density partitioning method confirms the superatomic molecule bonding framework of Au₃₈(SR)₂₄ in a straightforward manner.