Surface Structure and Electron Transfer Dynamics of the Self-Assembly of Cyanide on Au{111}

• Published in: Journal of physical chemistry. C Vol. 120; no. 47; pp. 26736 - 26746
• Main Authors: Guttentag, Andrew I, Wächter, Tobias, Barr, Kristopher K, Abendroth, John M, Song, Tze-Bin, Sullivan, Nichole F, Yang, Yang, Allara, David L, Zharnikov, Michael, Weiss, Paul S
• Format: Journal Article
• Language: English
• Published: American Chemical Society 01.12.2016
• Subjects: chemical bonding; cyanides; electron transfer; gold; spectroscopy
• ISSN: 1932-7447; 1932-7455; 1932-7455
• DOI: 10.1021/acs.jpcc.6b06006

A vibronic resonance between Au{111} surface states and adsorbed CN vibrations has been predicted, which we target for study. We have formed stable monolayers of cyanide on Au{111} and observe a hexagonal close-packed lattice with a nearest neighbor distance of 3.8 ± 0.5 Å. Cyanide orients normal to the surface attached via a Au–C bond. We show that the substrate–molecule coupling is particularly strong, leading to ultrafast electron transfer from the cyanide molecules to the Au{111} substrate as measured by resonant Auger spectroscopy using the core–hole clock method. The CN/Au{111} system is a simple example of a strongly interacting adsorbate–substrate system and will be the subject of a number of further studies, as discussed.