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Chemisorption of Atomic Oxygen on Pt(111) from DFT Studies of Pt-Clusters

Jacob, Timo and Muller, Richard P. and Goddard, William A., III (2003) Chemisorption of Atomic Oxygen on Pt(111) from DFT Studies of Pt-Clusters. Journal of Physical Chemistry B, 107 (35). pp. 9465-9476. ISSN 1520-6106. doi:10.1021/jp030716r.

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Using density functional theory (DFT) with gradient-corrected exchange-correlation functionals (B3LYP), we systematically study the electronic structure and bonding of oxygen to various Pt-clusters. Our aim is to understand how the cluster size and shape affect the chemistry of dispersed catalysts and to find the smallest cluster suitable for modeling surface reactions on the Pt(111)-surface. We find that the dependence of binding on the sites of these clusters is well described in terms of the interstitial electron model (IEM). The results show that the 28-atom three-layer Pt_(9.10.9)- cluster gives a good representation of the Pt(111)-surface for various adsorption sites. These results indicate that an O atom binds most strongly to the 3-fold hollow site with a binding energy of 3.28 eV for fcc and 2.95 eV for hcp. The binding energies for the other sites are 2.73 eV (bridge) and 2.02 eV (on-top). A one-layer 12-atom cluster does well at describing the bonding for all sites except the hcp site. These cluster results agree well with experimental results and with the best calculations on this surface:  all results agree that the η_3-fcc site is favored with a bond distance ≈ 2.01 Å. In addition, our calculated bond energy of 3.28 eV is consistent with experiment at low coverage (3.43 to 3.71 eV) and with the best DFT calculations on a surface (3.43 eV). We interpret the bonding of O to the η_3 sites (both fcc and hcp) in terms of the IEM localized covalent bonding model, in which the two singly occupied orbitals of O bond to singly occupied d orbitals of Pt, and the lone pair of p orbitals on the O coordinates to the third Pt of an η_3 site to form a donor−acceptor bond. This leads to two bonds of 2.01 Å and one of 2.21 Å.

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Goddard, William A., III0000-0003-0097-5716
Additional Information:© 2003 American Chemical Society. Received: June 5, 2003. Publication Date (Web): July 24, 2003. T.J. gratefully acknowledges support by the German academic exchange service (DAAD). This work was also supported by General Motors. The computation facilities of the MSC have been supported by grants from DURIP, NSF (MRI, CHE), and IBM-SUR. In addition, the MSC is supported by grants from DOE ASCI ASAP, ARO-MURI, NIH, ONR, ChevronTexaco, Beckman Institute, Seiko-Epson, Asahi Kasei, Avery-Dennison, Kellogg's, and 3M.
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Deutscher Akademischer Austauschdienst (DAAD)UNSPECIFIED
Office of Naval Research (ONR)UNSPECIFIED
Department of Energy (DOE)UNSPECIFIED
Army Research Office (ARO)UNSPECIFIED
Caltech Beckman InstituteUNSPECIFIED
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Issue or Number:35
Record Number:CaltechAUTHORS:20170510-110330755
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Official Citation:Chemisorption of Atomic Oxygen on Pt(111) from DFT Studies of Pt-Clusters Timo Jacob, Richard P. Muller, and William A. Goddard, III The Journal of Physical Chemistry B 2003 107 (35), 9465-9476 DOI: 10.1021/jp030716r
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:77343
Deposited By: Tony Diaz
Deposited On:16 May 2017 20:06
Last Modified:15 Nov 2021 17:30

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