A van der Waals DFT study of chain length dependence of alkanethiol adsorption on Au(111): Physisorption vs.chemisorption

The energetics and structures of physisorbed and chemisorbed alkanethiols on Au(111) have been systematically investigated up to 10 carbon atoms using van der Waals (vdW) corrected density functional theory (DFT) calculations. The role of chain length, tilting angle and coverage on the adsorption ch...

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Bibliographic Details
Published in:arXiv.org 2018-02
Main Authors: Ersen Mete, Yortanlı, Merve, Danışman, Mehmet Fatih
Format: Article
Language:English
Subjects:
Adsorption
Alkanes
Chains
Chemisorption
Density functional theory
Dependence
Gold
Organic chemistry
Surface chemistry
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Summary:The energetics and structures of physisorbed and chemisorbed alkanethiols on Au(111) have been systematically investigated up to 10 carbon atoms using van der Waals (vdW) corrected density functional theory (DFT) calculations. The role of chain length, tilting angle and coverage on the adsorption characteristics have been examined to elucidate the energetics and plausible transformation mechanisms between lying down and standing up phases. Coverage and size dependent chain-chain electronic interactions counteract with the alkyl chain-gold surface interactions and the surface relaxation of the metal in the formation of standing up monolayer structures. For the striped phases of long chain alkanethiols, however, our calculations on decanethiol indicates alkyl chain-gold surface interactions to be strong enough to force the molecule to be perfectly parallel to the surface by lifting a gold atom up, in agreement with the proposed models for this film in the literature.
ISSN:2331-8422
DOI:10.48550/arxiv.1802.10298