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The structure of the Au(111)/methylthiolate interface : new insights from near-edge X-ray absorption spectroscopy and X-ray standing waves

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Chaudhuri, Anindita, Odelius, Michael, Jones, R. G., Lee, Tien-Lin, Detlefs, B. and Woodruff, D. P.. (2009) The structure of the Au(111)/methylthiolate interface : new insights from near-edge X-ray absorption spectroscopy and X-ray standing waves. Journal of Chemical Physics, Vol.130 (No.12). p. 4708. ISSN 0021-9606

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Official URL: http://dx.doi.org/10.1063/1.3102095

Abstract

The local structure of the Au(111)([square root of]3×[square root of]3)R30°-methylthiolate surface phase has been investigated by S K-edge near-edge s-ray absorption fine structure (NEXAFS) both experimentally and theoretically and by experimental normal-incidence x-ray standing waves (NIXSW) at both the C and S atomic sites. NEXAFS shows not only excitation into the intramolecular sigma* S–C resonance but also into a sigma* S–Au orbital perpendicular to the surface, clearly identifying the local S headgroup site as atop a Au atom. Simulations show that it is not possible, however, to distinguish between the two possible adatom reconstruction models; a single thiolate species atop a hollow-site Au adatom or a dithiolate moiety comprising two thiolate species bonded to a bridge-bonded Au adatom. Within this dithiolate moiety a second sigma* S–Au orbital that lies near parallel to the surface has a higher energy that overlaps that of the sigma* S–C resonance. The new NIXSW data show the S–C bond to be tilted by 61° relative to the surface normal, with a preferred azimuthal orientation in <211>, corresponding to the intermolecular nearest-neighbor directions. This azimuthal orientation is consistent with the thiolate being atop a hollow-site Au adatom, but not consistent with the originally proposed Au-adatom-dithiolate moiety. However, internal conformational changes within this species could, perhaps, render this model also consistent with the experimental data.

Item Type:

Journal Article

Subjects:

Q Science > QC Physics

Divisions:

Faculty of Science > Physics

Library of Congress Subject Headings (LCSH):

Adsorption -- Research, Binding sites (Biochemistry), Self-assembly (Chemistry) -- Research, Thin films, Multilayered, X-ray absorption near edge structure

Journal or Publication Title:

Journal of Chemical Physics

Publisher:

American Institute of Physics

ISSN:

0021-9606

Official Date:

26 March 2009

Dates:

Date	Event
26 March 2009	Published

Volume:

Vol.130

Number:

No.12

Page Range:

p. 4708

Identification Number:

10.1063/1.3102095

Status:

Peer Reviewed

Access rights to Published version:

Open Access

Funder:

European Synchrotron Radiation Facility (ESRF)

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