Hexagons to Ribbons: Flipping Cyanide on Au{111}

Andrew I Guttentag; Kristopher K Barr; Tze-Bin Song; Kevin V Bui; Jacob N Fauman; Leticia F Torres; David D Kes; Adina Ciomaga; Jérôme Gilles; Nichole F Sullivan; Yang Yang; David L Allara; Michael Zharnikov; Paul S Weiss

doi:10.1021/jacs.6b06046

Hexagons to Ribbons: Flipping Cyanide on Au{111}

J Am Chem Soc. 2016 Dec 7;138(48):15580-15586. doi: 10.1021/jacs.6b06046. Epub 2016 Nov 23.

Authors

Andrew I Guttentag^{1

2}, Kristopher K Barr^{1

2}, Tze-Bin Song^{1

3}, Kevin V Bui^{4

5}, Jacob N Fauman^{4

6}, Leticia F Torres^{4

7}, David D Kes^{4

8}, Adina Ciomaga⁹, Jérôme Gilles¹⁰, Nichole F Sullivan¹¹, Yang Yang^{1

3}, David L Allara¹¹, Michael Zharnikov¹², Paul S Weiss^{1

2

3}

Affiliations

¹ California NanoSystems Institute, University of California, Los Angeles , Los Angeles, California 90095, United States.
² Department of Chemistry and Biochemistry, University of California, Los Angeles , Los Angeles, California 90095, United States.
³ Department of Material Science and Engineering, University of California, Los Angeles , Los Angeles, California 90095, United States.
⁴ Department of Mathematics, University of California, Los Angeles , Los Angeles, California 90095, United States.
⁵ Department of Industrial Engineering and Management Sciences, Northwestern University , Evanston, Illinois 60208, United States.
⁶ Department of Physics, University of California , Santa Barbara, California 93106, United States.
⁷ Department of Mathematics, University of San Francisco , San Francisco, California 94117, United States.
⁸ Department of Mathematics and Natural Sciences, California State University , Long Beach, California 90840, United States.
⁹ Department of Mathematics, Laboratoire Jacques Louis Lions, Université Paris Diderot , 5 Rue Thomas Mann, Paris 75013, France.
¹⁰ Department of Mathematics and Statistics, San Diego State University , San Diego, California 92182, United States.
¹¹ Department of Chemistry, Pennsylvania State University , University Park, Pennsylvania 16802, United States.
¹² Applied Physical Chemistry, Heidelberg University , 69120 Heidelberg, Germany.

PMID: 27934033
DOI: 10.1021/jacs.6b06046

Abstract

Cyanide monolayers on Au{111} restructure from a hexagonal close-packed lattice to a mixed-orientation "ribbon" structure through thermal annealing. The new surface structure loses most of the observed surface features characterizing the initial as-adsorbed system with "ribbon" domain boundaries isolating rotationally offset surface regions where the orientation is guided by the underlying gold lattice. A blue shift to higher frequencies of the CN vibration to 2235 cm^-1 with respect to the as-adsorbed CN/Au{111} vibration at 2146 cm^-1 is observed. In addition, a new low-frequency mode is observed at 145 cm^-1, suggesting a chemical environment change similar to gold-cyanide crystallization. We discuss this new structure with respect to a mixed cyanide/isocyanide monolayer and propose a bonding scheme consisting of Au-CN and Au-NC bound molecules that are oriented normal to the Au{111} surface.

Publication types

Research Support, U.S. Gov't, Non-P.H.S.
Research Support, Non-U.S. Gov't