Electron-hole pair effects in methane dissociative chemisorption on Ni(111)

The dissociative chemisorption of methane on metal surfaces has attracted much attention in recent years as a prototype of gas-surface reactions in understanding the mode specific and bond selective chemistry. In this work, we systematically investigate the influence of electron-hole pair excitation...

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Bibliographic Details
Published in:The Journal of chemical physics 2016-07, Vol.145 (4), p.044704-044704
Main Authors: Luo, Xuan, Jiang, Bin, Juaristi, J. Iñaki, Alducin, Maite, Guo, Hua
Format: Article
Language:English
Subjects:
Chemical bonds
CHEMISORPTION
Coefficient of friction
CRYSTAL LATTICES
CRYSTALS
Electrons
Energy dissipation
Energy of dissociation
EXCITATION
EXPERIMENTAL DATA
Friction
Holes (electron deficiencies)
INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
LANGEVIN EQUATION
Metal surfaces
METHANE
NICKEL
Organic chemistry
POTENTIAL ENERGY
REACTIVITY
Surface chemistry
Surface reactions
SURFACES
VIBRATIONAL STATES
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Summary:The dissociative chemisorption of methane on metal surfaces has attracted much attention in recent years as a prototype of gas-surface reactions in understanding the mode specific and bond selective chemistry. In this work, we systematically investigate the influence of electron-hole pair excitations on the dissociative chemisorption of CH4/CH3D/CHD3 on Ni(111). The energy dissipation induced by surface electron-hole pair excitations is modeled as a friction force introduced in the generalized Langevin equation, in which the independent atomic friction coefficients are determined within the local-density friction approximation. Quasi-classical trajectory calculations for CH4/CH3D/CHD3 have been carried out on a recently developed twelve-dimensional potential energy surface. Comparing the dissociation probabilities obtained with and without friction, our results clearly indicate that the electron-hole pair effects are generally small, both on absolute reactivity of each vibrational state and on the mode specificity and bond selectivity. Given similar observations in both water and methane dissociation processes, we conclude that electron-hole pair excitations would not play an important role as long as the reaction is direct and the interaction time between the molecule and metal electrons is relatively short.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.4959288