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Issue 1, 2006
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The chiroptical signature of achiral metal clusters induced by dissymmetric adsorbates

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Abstract

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.

Graphical abstract: The chiroptical signature of achiral metal clusters induced by dissymmetric adsorbates

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Publication details

The article was received on 15 Aug 2005, accepted on 31 Oct 2005 and first published on 17 Nov 2005


Article type: Communication
DOI: 10.1039/B511563A
Citation: Phys. Chem. Chem. Phys., 2006,8, 63-67
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    The chiroptical signature of achiral metal clusters induced by dissymmetric adsorbates

    M. Goldsmith, C. B. George, G. Zuber, R. Naaman, D. H. Waldeck, P. Wipf and D. N. Beratan, Phys. Chem. Chem. Phys., 2006, 8, 63
    DOI: 10.1039/B511563A

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