TY  - JOUR
AU  - Walter, M.
AU  - Akola, J.
AU  - Lopez-Acevedo, O.
AU  - Jadzinsky, P.D.
AU  - Calero, G.
AU  - Ackerson, C.J.
AU  - Whetten, R.L.
AU  - Grönbeck, H.
AU  - Häkkinen, H.
TI  - A unified view of ligand-protected gold clusters as superatom complexes
JO  - Proceedings of the National Academy of Sciences of the United States of America
VL  - 105
SN  - 0027-8424
CY  - Washington, DC
PB  - Academy
M1  - PreJuSER-1052
SP  - 9157 - 9162
PY  - 2008
N1  - Record converted from VDB: 12.11.2012
AB  - 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 (PR(3), X) ligands. The picture has emerged from analysis of large-scale density functional theory calculations of structurally characterized compounds, namely Au(102)(SR)(44), Au(39)(PR(3))(14)X(6)(-), Au(11)(PR(3))(7)X(3), and Au(13)(PR(3))(10)X(2)(3+), 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.
KW  - J (WoSType)
LB  - PUB:(DE-HGF)16
C6  - pmid:18599443
C2  - pmc:PMC2442568
UR  - <Go to ISI:>//WOS:000257645400007
DO  - DOI:10.1073/pnas.0801001105
UR  - https://juser.fz-juelich.de/record/1052
ER  -