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Agostic Interactions and Dissociation in the First Layer of Water on Pt(111)

Jacob, Timo and Goddard, William A., III (2004) Agostic Interactions and Dissociation in the First Layer of Water on Pt(111). Journal of the American Chemical Society, 126 (30). pp. 9360-9368. ISSN 0002-7863. doi:10.1021/ja049920y.

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Recent quantum mechanical (QM) calculations for a monolayer of H_2O on Ru(0001) suggested a novel stable structure with half the waters dissociated. However, different studies on Pt(111) suggested an undissociated bilayer structure in which the outer half of the water has the OH bonds toward the surface rather than the O lone pair. Since water layers on Pt are important in many catalytic processes (e.g., the fuel cell cathode), we calculated the energetics and structure of the first monolayer of water on the Pt(111) surface using QM [periodic slab using density functional calculations (DFT) with the PBE-flavor of exchange-correlation functional]. We find that the fully saturated surface (2/3 ML) has half the water almost parallel to the surface (forming a Pt−O Lewis acid−base bond), whereas the other half are perpendicular to the surface, but with the H down toward the surface (forming a Pt−HO agostic bond). This leads to a net bond energy of 0.60 eV/water = 13.8 kcal/mol (the standard ice model with the H up configuration of the water molecules perpendicular to the surface is less stable by 0.092 eV/water = 2.1 kcal/mol). We examined whether the partial dissociation of water proposed for Ru(0001) could occur on Pt(111). For the saturated water layer (2/3 ML) we find a stable structure with half the H_2O dissociated (forming Pt−OH and Pt−H covalent bonds), which is less favorable by only 0.066 eV/water = 1.51 kcal/mol. These results confirm the interpretation of combined experimental (XAS, XES, XPS) and theoretical (DFT cluster and periodic including spectrum calculations) studies, which find only the H down undissociated case. We find that the undissociated structure leads to a vertical displacement between the two layers of oxygens of ∼0.42 Å (for both H down and H up). In contrast, the partially dissociated system leads to a flat structure with a separation of the oxygen layers of 0.08 Å. Among the partially dissociated systems, we find that all subsurface positions for the dissociated hydrogen are less favorable than adsorbing on top of the free Pt surface atom. Our results suggest that for less than 1/3 ML, clustering would be observed rather than ordered monolayer structures.

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Goddard, William A., III0000-0003-0097-5716
Additional Information:© 2004 American Chemical Society. Received January 6, 2004. Publication Date (Web): July 10, 2004. We thank Prof. P. A. Thiel of Iowa State University for fruitful discussions and Dr. Peter Schultz from Sandia National Labs for the use of the SeqQuest PBC DFT code. T.J. gratefully acknowledges support by the German academic exchange service (DAAD). Additional support was provided by GM-GAPC and NSF-NIRT. The computation facilities of the MSC have been supported by grants from ARO-DURIP, ONR-DURIP, NSF (MRI, CHE), and IBM-SUR. In addition the MSC is supported by grants from DoE ASCI, ARO-MURI, ARO-DARPA, ONR-MURI, NIH, ONR, General Motors, ChevronTexaco, Seiko-Epson, Beckman Institute, and Asahi Kasei.
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Deutscher Akademischer Austauschdienst (DAAD)UNSPECIFIED
Army Research Office (ARO)UNSPECIFIED
Office of Naval Research (ONR)UNSPECIFIED
Department of Energy (DOE)UNSPECIFIED
Caltech Beckman InstituteUNSPECIFIED
Issue or Number:30
Record Number:CaltechAUTHORS:20170420-083648186
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Official Citation:Agostic Interactions and Dissociation in the First Layer of Water on Pt(111) Timo Jacob and and William A. Goddard III Journal of the American Chemical Society 2004 126 (30), 9360-9368 DOI: 10.1021/ja049920y
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:76751
Deposited By: Tony Diaz
Deposited On:20 Apr 2017 16:22
Last Modified:15 Nov 2021 17:02

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