|
|||||
|
|
Intermixed Adatom and Surface‐Bound Adsorbates in Regular Self‐Assembled Monolayers of Racemic 2‐Butanethiol on Au(111) |
|
| Authors: | Dr. Runhai Ouyang Dr. Jiawei Yan Dr. Palle S. Jensen Dr. Erhad Ascic Dr. Shiyu Gan Prof. David Tanner Prof. Bingwei Mao Prof. Li Niu Dr. Jingdong Zhang Dr. Chunguang Tang Prof. Noel S. Hush Prof. Jeffrey R. Reimers Prof. Jens Ulstrup |
| Affiliation: | 1. School of Chemistry F11, The University of Sydney, NSW 2006 (Australia);2. Department of Chemistry, Technical University of Denmark, Kongens Lyngby 2800 (Denmark);3. State Key Laboratory for Physical Chemistry of Solid Surfaces and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005 (China);4. State Key Laboratory of Electroanalytical Chemistry c/o Engineering Laboratory for Modern Analytical Techniques, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022 (China);5. University of Chinese Academy of Sciences, Beijing, 100049 (China);6. School of Molecular Bioscience, The University of Sydney, NSW 2006 (Australia);7. International Centre for Quantum and Molecular Structure, College of Sciences, Shanghai University, Shanghai 200444 (China).;8. School of Physics and Advanced Materials, The University of Technology Sydney, Sydney NSW 2007 (Australia) |
| Abstract: | In situ scanning tunneling microscopy combined with density functional theory molecular dynamics simulations reveal a complex structure for the self‐assembled monolayer (SAM) of racemic 2‐butanethiol on Au(111) in aqueous solution. Six adsorbate molecules occupy a (10×√3)R30° cell organized as two RSAuSR adatom‐bound motifs plus two RS species bound directly to face‐centered‐cubic and hexagonally close‐packed sites. This is the first time that these competing head‐group arrangements have been observed in the same ordered SAM. Such unusual packing is favored as it facilitates SAMs with anomalously high coverage (30 %), much larger than that for enantiomerically resolved 2‐butanethiol or secondary‐branched butanethiol (25 %) and near that for linear‐chain 1‐butanethiol (33 %). |
| Keywords: | density functional theory dispersion scanning tunneling microscopy steric effects thiolate |