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

Michael Walter, Jaakko Akola, Olga Lopez-Acevedo, Pablo D. Jadzinsky, Guillermo Calero, Christopher J. Ackerson, Robert L. Whetten, Henrik Grönbeck, Hannu Häkkinen

Research output: Contribution to journalArticlepeer-review

1414 Scopus citations


Synthesis, characterization, and functionalization of self-assembled, ligand-stabilized gold nanoparticles are long-standing issues in the chemistry of nanomaterials. Factors driving the thermodynamic stability of well documented discrete sizes are largely unknown. Herein, we provide a unified view of principles that underlie the stability of particles protected by thiolate (SR) or phosphine and halide (PR3, X) ligands. The picture has emerged from analysis of large-scale density functional theory calculations of structurally characterized compounds, namely Au102(SR)44, Au39(PR3)14X6-, Au 11(PR3)7X3, and Au 13(PR3)10X23+, where X is either a halogen or a thiolate. Attributable to a compact, symmetric core and complete steric protection, each compound has a filled spherical electronic shell and a major energy gap to unoccupied states. Consequently, the exceptional stability is best described by a "noble-gas superatom" analogy. The explanatory power of this concept is shown by its application to many monomeric and oligomeric compounds of precisely known composition and structure, and its predictive power is indicated through suggestions offered for a series of anomalously stable cluster compositions which are still awaiting a precise structure determination.

Original languageEnglish (US)
Pages (from-to)9157-9162
Number of pages6
JournalProceedings of the National Academy of Sciences of the United States of America
Issue number27
StatePublished - Jul 8 2008
Externally publishedYes


  • Density functional theory monolayer-protected cluster

ASJC Scopus subject areas

  • General


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