Dash, LK and Gillan, MJ (2004) Assessment of competing mechanisms of the abstraction of hydrogen from CH4 on Li/MgO(001). SURF SCI , 549 (3) 217 - 226. 10.1016/j.susc.2003.11.008.
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First-principles calculations based on the density functional theory (DFT)-pseudopotential method with plane wave basis sets are used to study the energetics of H abstraction from CH4 on the Li-doped MgO(0 0 1) surface. Experimental work has led to the proposal of two competing mechanisms for the reaction: either direct interaction of CH4 with an O- hole state bound to the Li dopant, or interaction of CH4 with a surface F-centre whose charge state is modified by the presence of the dopant. The calculations are performed in periodically repeated slab geometry, with attention given to system-size errors. For direct interaction with the hole state, the calculations indicate that the reaction is weakly endothermic, by about 0.2 eV, but for the F-centre mechanism it is endothermic by over I eV. Even allowing for likely DFT errors of a few tenths of an electron volt, this gives strong evidence against the F-centre mechanism. (C) 2003 Elsevier B.V. All rights reserved.
|Title:||Assessment of competing mechanisms of the abstraction of hydrogen from CH4 on Li/MgO(001)|
|Keywords:||density functional calculations, magnesium oxides, alkanes, catalysis, ELECTRONIC-STRUCTURE, MGO(001) SURFACE, ACTIVE-SITES, AB-INITIO, METHANE, MGO, PSEUDOPOTENTIALS, ENERGETICS, FORMALISM, CATALYSTS|
|UCL classification:||UCL > School of BEAMS > Faculty of Maths and Physical Sciences > London Centre for Nanotechnology|
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