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CO adsorption on CeO2(110) using hybrid-DFT embedded-cluster calculations
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Materials Chemistry, Structural Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Materials Chemistry, Structural Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Materials Chemistry, Structural Chemistry.
2006 (English)In: Chemical Physics, ISSN 0301-0104, E-ISSN 1873-4421, Vol. 328, no 1-3, 345-353 p.Article in journal (Refereed) Published
Abstract [en]

The adsorption of CO on the CeO2 (110) surface has been studied using hybrid density functional theory (DFT) in the form of the B3LYP functional. In our calculations, both physisorption and chemisorption are observed. In the physisorption case, CO binds perpendicularly to a surface Ce ion. The adsorption energy is estimated to 0.1 eV and the CO stretching vibration becomes slightly blue-shifted (+9 cm(-1)), but the changes to the substrate and adsorbate structure are minimal. Test calculations using Moller-Plesset perturbation theory to the second order (MP2) suggest that dispersive interactions may be important in the case of CO physisorption on ceria. A chemisorption site was also found, where the CO molecule binds to two surface O ions, forming a surface carbonate species. Here, B3LYP predicts an adsorption energy of 2.1 eV and a red-shift of 470 cm(-1) for the CO stretching vibration.

Place, publisher, year, edition, pages
2006. Vol. 328, no 1-3, 345-353 p.
Keyword [en]
CO adsorption, ceria, hybrid-DFT, embedded-cluster calculations
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:uu:diva-93856DOI: 10.1016/j.chemphys.2006.07.022ISI: 000241179500044OAI: oai:DiVA.org:uu-93856DiVA: diva2:167474
Available from: 2005-12-23 Created: 2005-12-23 Last updated: 2017-12-14Bibliographically approved
In thesis
1. Combined Molecular Dynamics and Embedded-Cluster Calculations in Metal Oxide Surface Chemistry
Open this publication in new window or tab >>Combined Molecular Dynamics and Embedded-Cluster Calculations in Metal Oxide Surface Chemistry
2005 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The development and improvement of the functionality of metal oxides in heterogeneous catalysis and other surface chemical processes can greatly benefit from an atomic-level understanding of the surface chemistry. Atomistic calculations such as quantum mechanical (QM) calculations and molecular dynamics (MD) simulations can provide highly detailed information about the atomic and electronic structure, and constitute valuable complements to experimental surface science techniques.

In this thesis, an embedded-cluster approach for quantum mechanical calculations has been developed to model the surface chemistry of metal oxides. In particular, CO adsorption on the MgO(001) and CeO2(110) surfaces as well as O vacancy formation at the CeO2(110) surface have been investigated. The cluster model has been thoroughly tested by comparison with electronic structure calculations for the periodic slab model.

The chemical implications of distorted surface structures arising from the surface dynamics have been investigated by combining the QM embedded-cluster calculations with force-field based MD simulations. Here QM embedded-cluster calculations were performed using surface structures sampled from the MD simulations.

This combined MD+QM embedded-cluster procedure was applied to the CO adsorption on MgO(001) at 50 K and the O vacancy formation on CeO2(110) at 300 K. Significant thermal variations of the CO adsorption energy and the O vacancy formation energy were observed. It was found that these variations could be estimated using the force field of the MD simulation as an interaction model. With this approach, the QM results were extrapolated to higher temperature and doped systems.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2005. 52 p.
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 130
Keyword
Inorganic chemistry, embedded-cluster, ab initio, molecular dynamics, metal oxide, ceria, magnesium oxide, adsorption, surface defect, Oorganisk kemi
National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:uu:diva-6227 (URN)91-554-6422-X (ISBN)
Public defence
2006-01-19, Room 2001, Ångströmlaboratoriet, Lägerhyddsvägen 1, Uppsala, 10:15
Opponent
Supervisors
Available from: 2005-12-23 Created: 2005-12-23 Last updated: 2013-09-18Bibliographically approved

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Herschend, BjörnHermansson, Kersti

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