A1 Journal article (refereed)
A hollow tetrahedral cage of hexadecagold dianion provides a robust backbone for a tuneable sub-nanometer oxidation and reduction agent via endohedral doping (2006)

Walter, M., & Häkkinen, H. (2006). A hollow tetrahedral cage of hexadecagold dianion provides a robust backbone for a tuneable sub-nanometer oxidation and reduction agent via endohedral doping. Physical Chemistry Chemical Physics, 8(46), 5407-5411. https://doi.org/10.1039/B612221C

JYU authors or editors

Publication details

All authors or editors: Walter, Michael; Häkkinen, Hannu

Journal or series: Physical Chemistry Chemical Physics

ISSN: 1463-9076

eISSN: 1463-9084

Publication year: 2006

Volume: 8

Issue number: 46

Pages range: 5407-5411

Publisher: Royal Society of Chemistry

Publication country: United Kingdom

Publication language: English

DOI: https://doi.org/10.1039/B612221C

Publication open access: Not open

Publication channel open access: 

Abstract

We show, via density functional theory calculations, that dianionic Au162− 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.

Keywords: nanostructures; physical chemistry

Contributing organizations

Ministry reporting: Yes

Preliminary JUFO rating: Not rated