The mechanism of chemisorption of hydrogen atom on graphene: insights from the reaction force and reaction electronic flux

At the PBE-D3/cc-pVDZ level of theory, the hydrogen chemisorption on graphene was analyzed using the reaction force and reaction electronic flux (REF) theories in combination with electron population analysis. It was found that chemisorption energy barrier is mainly dominated by structural work (∼73...

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Bibliographic Details
Published in:The Journal of chemical physics 2014-10, Vol.141 (13), p.134701-134701
Main Authors: Cortés-Arriagada, Diego, Gutiérrez-Oliva, Soledad, Herrera, Bárbara, Soto, Karla, Toro-Labbé, Alejandro
Format: Article
Language:English
Subjects:
ADSORBENTS
ATOMS
Charge transfer
CHEMISORPTION
DESORPTION
DIFFUSION BARRIERS
ELECTRONS
GRAPHENE
HYBRIDIZATION
Hydrogen bonds
Hydrogen storage
INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
MAGNETIZATION
NANOSCIENCE AND NANOTECHNOLOGY
Organic chemistry
Physics
Reconstruction
SUBSTRATES
Surface chemistry
SURFACES
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Summary:At the PBE-D3/cc-pVDZ level of theory, the hydrogen chemisorption on graphene was analyzed using the reaction force and reaction electronic flux (REF) theories in combination with electron population analysis. It was found that chemisorption energy barrier is mainly dominated by structural work (∼73%) associated to the substrate reconstruction whereas the electronic work is the greatest contribution of the reverse energy barrier (∼67%) in the desorption process. Moreover, REF shows that hydrogen chemisorption is driven by charge transfer processes through four electronic events taking place as H approaches the adsorbent surface: (a) intramolecular charge transfer in the adsorbent surface; (b) surface reconstruction; (c) substrate magnetization and adsorbent carbon atom develops a sp(3) hybridization to form the σC-H bond; and (d) spontaneous intermolecular charge transfer to reach the final chemisorbed state.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.4896611