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The Role of Gold Adatoms and Stereochemistry in Self-Assembly of Methylthiolate on Au(111)

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/ja902629y· OSTI ID:964342
 [1];  [1];  [2];  [3]
  1. University of Sherbrooke
  2. University of Virginia, Charlottesville
  3. ORNL

On the basis of high resolution STM images and DFT modeling, we have resolved low- and high-coverage structures of methylthiolate (CH3S) self-assembled on the Au(111) surface. The key new finding is that the building block of all these structures has the same stoichiometry of two thiolate species joined by a gold adatom. The self-arrangement of the methylthiolate?adatom complexes on the surface depends critically on their stereochemical properties. Variations of the latter can produce local ordering of adatom complexes with either (3 x 4) or (3 x 4{radical}3) periodicity. A possible structural connection between the (3 x 4{radical}3) structure and commonly observed ({radical}3 x {radical}3)R30{sup o} phase in methylthiolate self-assembled monolayers is developed by taking into account the reduction in the long-range order and stereochemical isomerization at high coverage. We also suggest how the observed self-arrangements of methylthiolate may be related to the c(4 x 2) phase of its longer homologues.

Research Organization:
Oak Ridge National Laboratory (ORNL); Center for Nanophase Materials Sciences
Sponsoring Organization:
SC USDOE - Office of Science (SC)
DOE Contract Number:
AC05-00OR22725
OSTI ID:
964342
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 12989 Vol. 36; ISSN JACSAT; ISSN 0002-7863
Country of Publication:
United States
Language:
English

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