Electronic and optical properties of the Au22[1,8-bis(diphenylphosphino) octane]6 nanoclusters disclosed by DFT and TD-DFT calculations

Francesco Muniz-Miranda, Davide Presti, Maria Cristina Menziani, Alfonso Pedone

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15 Scopus citations


Time-dependent density functional theory calculations have been used to investigate the electronic and optical properties of a nanocluster composed of two directly bonded Au11 subunits, held together by six bidentate diphosphine ligands: 1,8-bis(diphenylphosphino) octane. Three exchange–correlation functionals have been adopted, a general hybrid (PBE0) and two range-separated hybrids (ωB97X and CAM-B3LYP). The results obtained show that the aforementioned properties are significantly different from those of a previously studied Au11-based nanocluster formed by just one single subunit. In particular, charge transfer excitations from the inner metal core to the outer ligands affect most of the UV–visible spectrum and occur for both alkyl and aromatic ligands. This is particularly evident when thiazole molecules are bonded to the gold core: In this case Au → ligand transitions affect also the first HOMO → LUMO excitation. Moreover, the gold core of this Au22 nanocluster has eight under-coordinated Au surface atoms not engaged in bonds with the ligands. No other known organic-protected gold nanocluster has a similar feature. These gold atoms can be considered as potential in situ active sites for catalysis, their catalytic efficiency and selectivity being modulated by charge distribution.

Original languageEnglish (US)
Article number5
Pages (from-to)1-9
Number of pages9
JournalTheoretical Chemistry Accounts
Issue number1
StatePublished - Jan 1 2016

Bibliographical note

Funding Information:
This work was supported by the Italian “Ministero dell’Istruzione, dell’Università e della Ricerca” (MIUR) through the “Futuro in Ricerca” (FIRB) Grant RBFR1248UI_002 entitled “Novel Multiscale Theorethical/Computational Strategies for the Design of Photo and Thermo responsive Hybrid Organic–Inorganic Components for Nanoelectronic Circuits,” and the “Programma di ricerca di relevante interesse nazionale” (PRIN) Grant 2010C4R8M8 entitled “Nanoscale functional Organization of (bio)Molecules and Hybrids for targeted Application in Sensing, Medicine and Biotechnology” is also acknowledged. CINECA granted computation time within the research project AUNANMR-HP10CJ027S.

Publisher Copyright:
© 2015, Springer-Verlag Berlin Heidelberg.


  • DFT
  • Gold nanoclusters


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