6533b82dfe1ef96bd12913a0
RESEARCH PRODUCT
A critical size for emergence of nonbulk electronic and geometric structures in dodecanethiolate-protected Au clusters.
Wataru KurashigeHannu HäkkinenYoshiki NiihoriTafu NakazakiShinjiro TakanoSeiji YamazoeSeiji YamazoeSami MalolaYuichi NegishiTatsuya TsukudaTatsuya Tsukudasubject
absorption spectroscopygeometryAbsorption spectroscopyta114high performance liquid chromatographyChemistryGeneral Chemistrygoldelectronic structureBiochemistryCatalysisCombined approachCrystallographyColloid and Surface Chemistrylight absorptionliquid chromatographyDensity functional theoryStructured modelta116electromagnetic wave absorptiondensity functional theorydescription
We report on how the transition from the bulk structure to the cluster-specific structure occurs in n-dodecanethiolate-protected gold clusters, Au(n)(SC12)m. To elucidate this transition, we isolated a series of Au(n)(SC12)m in the n range from 38 to ∼520, containing five newly identified or newly isolated clusters, Au104(SC12)45, Au(∼226)(SC12)(∼76), Au(∼253)(SC12)(∼90), Au(∼356)(SC12)(∼112), and Au(∼520)(SC12)(∼130), using reverse-phase high-performance liquid chromatography. Low-temperature optical absorption spectroscopy, powder X-ray diffractometry, and density functional theory (DFT) calculations revealed that the Au cores of Au144(SC12)60 and smaller clusters have molecular-like electronic structures and non-fcc geometric structures, whereas the structures of the Au cores of larger clusters resemble those of the bulk gold. A new structure model is proposed for Au104(SC12)45 based on combined approach between experiments and DFT calculations.
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2014-12-31 | Journal of the American Chemical Society |