Methane dissociation on Pt(111): Searching for a specific reaction parameter density functional

The theoretical description of methane dissociating on metal surfaces is a current frontier in the field of gas-surface dynamics. Dynamical models that aim at achieving a highly accurate description of this reaction rely on potential energy surfaces based on density functional theory calculations at...

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Bibliographic Details
Published in:The Journal of chemical physics 2016-01, Vol.144 (4), p.044702-044702
Main Authors: Nattino, Francesco, Migliorini, Davide, Bonfanti, Matteo, Kroes, Geert-Jan
Format: Article
Language:English
Subjects:
CRYSTAL STRUCTURE
DENSITY FUNCTIONAL METHOD
Density functional theory
DISSOCIATION
Exchanging
INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
Metal surfaces
METHANE
Molecular dynamics
MOLECULAR DYNAMICS METHOD
Parameters
Physics
PLATINUM
POTENTIAL ENERGY
QUANTUM STATES
REACTIVITY
Searching
Surface dynamics
SURFACES
TEMPERATURE DEPENDENCE
VAN DER WAALS FORCES
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Summary:The theoretical description of methane dissociating on metal surfaces is a current frontier in the field of gas-surface dynamics. Dynamical models that aim at achieving a highly accurate description of this reaction rely on potential energy surfaces based on density functional theory calculations at the generalized gradient approximation. We focus here on the effect that the exchange-correlation functional has on the reactivity of methane on a metal surface, using CHD3 + Pt(111) as a test case. We present new ab initio molecular dynamics calculations performed with various density functionals, looking also at functionals that account for the van der Waals (vdW) interaction. While searching for a semi-empirical specific reaction parameter density functional for this system, we find that the use of a weighted average of the PBE and the RPBE exchange functionals together with a vdW-corrected correlation functional leads to an improved agreement with quantum state-resolved experimental data for the sticking probability, compared to previous PBE calculations. With this semi-empirical density functional, we have also investigated the surface temperature dependence of the methane dissociation reaction and the influence of the rotational alignment on the reactivity, and compared our results with experiments.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.4939520