A unified view of ligand-protected gold clusters as superatom complexes

A unified view of ligand-protected gold clusters as superatom complexes

July 8, 2008 | Michael Walter†, Jaakko Akola†*, Olga Lopez-Acevedo†, Pablo D. Jadzinsky§†, Guillermo Calero§, Christopher J. Ackerson§†, Robert L. Whetten††, Henrik Grönbeck‡‡, and Hannu Häkkinen†§§†††
The article provides a unified view of the stability of ligand-protected gold clusters, particularly those stabilized by thiolate (SR) or phosphine and halide (PR3)X ligands. Through large-scale density functional theory (DFT) calculations, the authors analyze several structurally characterized compounds, including Au103(PR3)44, Au33(PR3)34X6−, Au11(PR3)2X, and Au15(PR3)10X2+, where X is either a halogen or a thiolate. These compounds exhibit a compact, symmetric core and complete steric protection, resulting in a filled spherical electronic shell and a significant energy gap to unoccupied states. This stability is attributed to the "noble-gas superatom" analogy, where the core has a closed-shell configuration similar to noble gases. The concept is applied to various monomeric and oligomeric compounds, and its predictive power is demonstrated through suggestions for stable cluster compositions awaiting precise structural determination. The study also discusses the relevance of these findings to the identification of other all-thiolate-protected gold clusters and the importance of the atomic structure at the interface between the gold core and the gold-thiolate shell.The article provides a unified view of the stability of ligand-protected gold clusters, particularly those stabilized by thiolate (SR) or phosphine and halide (PR3)X ligands. Through large-scale density functional theory (DFT) calculations, the authors analyze several structurally characterized compounds, including Au103(PR3)44, Au33(PR3)34X6−, Au11(PR3)2X, and Au15(PR3)10X2+, where X is either a halogen or a thiolate. These compounds exhibit a compact, symmetric core and complete steric protection, resulting in a filled spherical electronic shell and a significant energy gap to unoccupied states. This stability is attributed to the "noble-gas superatom" analogy, where the core has a closed-shell configuration similar to noble gases. The concept is applied to various monomeric and oligomeric compounds, and its predictive power is demonstrated through suggestions for stable cluster compositions awaiting precise structural determination. The study also discusses the relevance of these findings to the identification of other all-thiolate-protected gold clusters and the importance of the atomic structure at the interface between the gold core and the gold-thiolate shell.
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[slides and audio] A unified view of ligand-protected gold clusters as superatom complexes