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

Literature Information

Publication Date 2017-04-26
DOI 10.1039/C7CP01653K
Impact Factor 3.676
Authors

Ersen Mete, Merve Yortanlı, Mehmet Fatih Danışman


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Abstract

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 has 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 indicate 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.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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