The adsorption of CO on charged and neutral Au and Au2: a comparison between wave-function based and density functional theory.

Full Abstract

Quantum theoretical calculations are presented for CO attached to charged and neutral Au and Au(2) with the aim to test the performance of currently applied density functional theory (DFT) by comparison with accurate wave-function based results. For this, we developed a compact sized correlation-consistent valence basis set which accompanies a small-core energy-consistent scalar relativistic pseudopotential for gold. The properties analyzed are geometries, dissociation energies, vibrational frequencies, ionization potentials, and electron affinities. The important role of the basis-set superposition error is addressed which can be substantial for the negatively charged systems. The dissociation energies decrease along the series Au(+)-CO, Au-CO, and Au(-)-CO and as well as along the series Au(2)(+)-CO, Au(2)-CO, and Au(2)(-)-CO. As one expects, a negative charge on gold weakens the carbon oxygen bond considerably, with a consequent redshift in the CO stretching frequency when moving from the positively charged to the neutral and the negatively charged gold atom or dimer. We find that the different density functional approximations applied are not able to correctly describe the rather weak interaction between CO and gold, thus questioning the application of DFT to CO adsorption on larger gold clusters or surfaces.

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Author information

Author/s: Schwerdtfeger, Peter (P); Lein, Matthias (M); Krawczyk, Robert P (RP); Jacob, Christoph R (CR);

Affiliation: Center of Theoretical Chemistry and Physics, The New Zealand Institute for Advanced Study, Massey University (Auckland Campus), Private Bag 102904, North Shore MSC, Auckland, New Zealand. p.a.schwerdtfeger(-atsign-)massey.ac.nz

Journal and publication information

Publication Type: Comparative Study; Journal Article; Research Support, Non-U.S. Gov't

Journal: The Journal of chemical physics (J Chem Phys), published in United States. (Language: eng)

Reference: 2008-Mar; vol 128 (issue 12) : pp 124302

Dates: Created 2008/04/01; Completed 2008/06/19;

PMID: 18376914, status: MEDLINE (last retrieval date: 11/6/2008)

Sourced from the National Library of Medicine. Abstract text and other information may be subject to copyright.

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MeSH headings (categories)

This article was linked to the MESH Headings shown below.

Adsorption
Carbon Monoxide - chemistry
Gold - chemistry

Associated Chemicals: Carbon Monoxide (630-08-0) ; Gold (7440-57-5)

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