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The chiroptical signature of achiral metal clusters induced by dissymmetric adsorbates

Goldsmith, MR and George, CB and Zuber, G and Naaman, R and Waldeck, DH and Wipf, P and Beratan, DN (2006) The chiroptical signature of achiral metal clusters induced by dissymmetric adsorbates. Physical Chemistry Chemical Physics, 8 (1). 63 - 67. ISSN 1463-9076

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Using a dissymmetrically-perturbed particle-in-a-box model, we demonstrate that the induced optical activity of chiral monolayer protected clusters, such as Whetten's Au28(SG)16 glutathione-passivated gold nanoclusters (J. Phys. Chem. B, 2000, 104, 2630-2641), could arise from symmetric metal cores perturbed by a dissymmetric or chiral field originating from the adsorbates. This finding implies that the electronic states of the nanocluster core are chiral, yet the lattice geometries of these cores need not be geometrically distorted by the chiral adsorbates. Based on simple chiral monolayer protected cluster models, we rationalize how the adsorption pattern of the tethering sulfur atoms has a substantial effect on the induced CD in the NIR spectral region, and we show how the chiral image charge produced in the core provides a convenient means of visualizing dissymmetric perturbations to the achiral gold nanocluster core. © the Owner Societies 2006.


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Item Type: Article
Status: Published
CreatorsEmailPitt UsernameORCID
Goldsmith, MR
George, CB
Zuber, G
Naaman, R
Waldeck, DHdave@pitt.eduDAVE
Wipf, Ppwipf@pitt.eduPWIPF
Beratan, DN
Date: 6 April 2006
Date Type: Publication
Journal or Publication Title: Physical Chemistry Chemical Physics
Volume: 8
Number: 1
Page Range: 63 - 67
DOI or Unique Handle: 10.1039/b511563a
Schools and Programs: Dietrich School of Arts and Sciences > Chemistry
Refereed: Yes
ISSN: 1463-9076
MeSH Headings: Adsorption; Computer Simulation; Gold--chemistry; Models, Chemical; Models, Molecular; Stereoisomerism; Sulfides
PubMed ID: 16482245
Date Deposited: 30 Oct 2013 16:52
Last Modified: 22 Jun 2021 12:55


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