Kinetic parameters from temperature programmed desorption spectra combined with energy relations: top and bridge CO on Rh(100)

• Published in: Physical chemistry chemical physics : PCCP Vol. 12; no. 28; pp. 853 - 861
• Main Authors: Jansen, Maarten M. M, Hermse, Chrétien G. M, Jansen (Tonek), A. P. J
• Format: Journal Article
• Language: English
• Published: Cambridge Royal Society of Chemistry 28.07.2010
• Subjects: Chemistry; Exact sciences and technology; General and physical chemistry; Surface physical chemistry; Trace; Monte Carlo method; Adsorption; Energy; Saturation; Theoretical study; Thermodesorption; Desorption; Kinetic parameter; Structure
• ISSN: 1463-9076; 1463-9084
• DOI: 10.1039/b926380b

A Monte Carlo model of CO on Rh(100) is presented that can correctly describe CO adsorption and desorption over the entire coverage region: from 0 ML to saturation coverage (0.83 ML). Experimental temperature-programmed desorption traces are fitted with simulated traces by differential evolution to obtain numerical values of kinetic parameters. Energy relations are used to limit the amount of fitted parameter sets to only include sets which can reproduce the experimentally observed adlayer structures. The fit that best approaches the actual kinetic parameters uses additional relations to improve the position of the desorption features. In both cases, an exact fit between the experimental and simulated desorption traces is not obtained. Because of this, the magnitude of the obtained kinetic parameters is determined only qualitatively. The desorption of CO on Rh(100) is modelled up to 0.83 ML with kMC using energy relations and a differential evolution fitting procedure.