This article presents a unified view of ligand-protected gold clusters as superatom complexes. The study analyzes the stability of gold nanoparticles protected by thiolate (SR) or phosphine and halide (PR₃, X) ligands. Using large-scale density functional theory calculations, the researchers show that these clusters have filled spherical electronic shells and major energy gaps to unoccupied states, similar to noble gases. This suggests that these clusters can be described as "noble-gas superatoms." The concept is applied to various monomeric and oligomeric compounds, and its predictive power is demonstrated through suggestions for anomalously stable cluster compositions. The study also discusses the electronic structure of the 102-atom gold cluster, Au₁₀₂(p-MBA)₄₄, which is protected by a gold-thiolate layer. The cluster has a core of 79 gold atoms and a protective layer of 23 gold atoms. The electronic structure analysis shows that the core has a closed electron shell and a significant HOMO-LUMO gap, indicating electronic stability. The protective layer is composed of RS-(AuSR) units that localize electrons from the core to form surface chemical bonds. The study also examines the phosphine-halide-protected 39-atom gold cluster, Au₃₉(PR₃)₁₄X₆⁻, and the undecagold and tridecagold compounds. These clusters are shown to have closed electron shells and significant HOMO-LUMO gaps, consistent with the superatom concept. The study highlights the importance of the electronic structure and steric protection in the stability of these clusters. The research also discusses the connection between the structure of the Au₁₀₂(p-MBA)₄₄ cluster and the interface of the bulk Au(111) surface and self-assembled monolayers (SAMs). The findings suggest that the electronic structure of these clusters can be understood through the superatom concept, which has implications for the design and application of nanomaterials. The study provides a solid foundation for understanding the distinct electrical, optical, and chemical properties of monolayer-protected gold nanoclusters (MPCs), which can be used in various applications such as catalysis, sensing, photonics, biolabeling, and molecular electronics.This article presents a unified view of ligand-protected gold clusters as superatom complexes. The study analyzes the stability of gold nanoparticles protected by thiolate (SR) or phosphine and halide (PR₃, X) ligands. Using large-scale density functional theory calculations, the researchers show that these clusters have filled spherical electronic shells and major energy gaps to unoccupied states, similar to noble gases. This suggests that these clusters can be described as "noble-gas superatoms." The concept is applied to various monomeric and oligomeric compounds, and its predictive power is demonstrated through suggestions for anomalously stable cluster compositions. The study also discusses the electronic structure of the 102-atom gold cluster, Au₁₀₂(p-MBA)₄₄, which is protected by a gold-thiolate layer. The cluster has a core of 79 gold atoms and a protective layer of 23 gold atoms. The electronic structure analysis shows that the core has a closed electron shell and a significant HOMO-LUMO gap, indicating electronic stability. The protective layer is composed of RS-(AuSR) units that localize electrons from the core to form surface chemical bonds. The study also examines the phosphine-halide-protected 39-atom gold cluster, Au₃₉(PR₃)₁₄X₆⁻, and the undecagold and tridecagold compounds. These clusters are shown to have closed electron shells and significant HOMO-LUMO gaps, consistent with the superatom concept. The study highlights the importance of the electronic structure and steric protection in the stability of these clusters. The research also discusses the connection between the structure of the Au₁₀₂(p-MBA)₄₄ cluster and the interface of the bulk Au(111) surface and self-assembled monolayers (SAMs). The findings suggest that the electronic structure of these clusters can be understood through the superatom concept, which has implications for the design and application of nanomaterials. The study provides a solid foundation for understanding the distinct electrical, optical, and chemical properties of monolayer-protected gold nanoclusters (MPCs), which can be used in various applications such as catalysis, sensing, photonics, biolabeling, and molecular electronics.