Size-dependent structural evolution and chemical reactivity of gold clusters

作者：Yoon Bokwon; Koskinen Pekka; Huber Bernd; Kostko Oleg; von Issendorff Bernd; Hakkinen Hannu; Moseler Michael^*; Landman Uzi

来源：ChemPhysChem, 2007, 8(1): 157-161.

DOI：10.1002/cphc.200600524

• chemical reactivity
• density functional calculations
• gold photoelectron spectroscopy
• structure elucidation

Ground-state structures and other experimentally relevant isomers of Au-15(-) to Au-24(-) clusters are determined through joint first-principles density functional theory and photoelectron spectroscopy measurements. Subsequent calculations of molecular O-2 adsorption to the optimal cluster structures reveal a size-dependent reactivity pattern that agrees well with earlier experiments. A detailed analysis of the underlying electronic structure shows that the chemical reactivity of the gold cluster anions can be elucidated in terms of a partial-jellium picture, where delocalized electrons occupying electronic shells move over the ionic skeleton, whose geometric structure is strongly influenced by the directional bonding associated with the highly localized "d-band" electrons.

• 出版日期2007-1-8