6533b7d6fe1ef96bd1267183
RESEARCH PRODUCT
A hollow tetrahedral cage of hexadecagold dianion provides a robust backbone for a tuneable sub-nanometer oxidation and reduction agent via endohedral doping.
Michael WalterHannu Haekkinensubject
ChemistryBinding energyDopingGeneral Physics and AstronomyGeneral MedicineRedoxIonCrystallographyDelocalized electronComputational chemistryChemical physicsTetrahedronCluster (physics)NanometreDensity functional theoryPhysical and Theoretical ChemistryTriplet stateCageValence electrondescription
We show, via density functional theory calculations, that dianionic Au16(2-) cluster has a stable, hollow, Td symmetric cage structure, stabilized by 18 delocalized valence electrons. The cage maintains its robust geometry, with a minor Jahn-Teller deformation, over several charge states (q = -1,0,+1), forming spin doublet, triplet and quadruplet states according to the Hund's rules. Endohedral doping of the Au16 cage by Al or Si yields a geometrically robust, tuneable oxidation and reduction agent. Si@Au16 is a magic species with 20 delocalized electrons. We calculate a significant binding energy for the anionic Si@Au16/O2- complex and show that the adsorbed O2 is activated to a superoxo-species, a result which is at variance with the experimentally well-documented inertness of Au16- anion towards oxygen uptake.
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2007-02-20 | Physical chemistry chemical physics : PCCP |