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Understanding the properties of interfaces between organic self‐assembled monolayers and noble metals—a theoretical perspective
Author(s) -
Rangger Gerold M.,
Romaner Lorenz,
Heimel Georg,
Zojer Egbert
Publication year - 2008
Publication title -
surface and interface analysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.52
H-Index - 90
eISSN - 1096-9918
pISSN - 0142-2421
DOI - 10.1002/sia.2645
Subject(s) - self assembled monolayer , monolayer , chemistry , molecular electronics , molecule , molecular orbital , biphenyl , chemical physics , noble metal , nanotechnology , atomic orbital , orbital hybridisation , metal , computational chemistry , crystallography , materials science , molecular orbital theory , physics , organic chemistry , quantum mechanics , electron
Highly ordered, self‐assembled monolayers (SAMs) on (noble) metal surfaces are of particular importance for both the emerging field of single‐molecule electronics as well as for improving the characteristics of more conventional organic (opto)electronic devices. In the first part of this article, we review the microscopic description of electrode work function modification induced by SAMs and the alignment of molecular states relative to the states in the metal. The focus will be on the Ag(111) surface and biphenyl SAMs involving different donor–acceptor head‐group substituents. The impact of different docking groups will also be discussed and the results will be compared to previous findings (primarily) for SAMs on Au(111). The second part of the article deals with an in‐depth description of charge rearrangements and the hybridization between molecular and metal states by projecting the electronic states of the combined system onto the orbitals of the isolated molecules. Furthermore, the sulfur–silver bond is analyzed by means of a crystal orbital occupation population analysis. Copyright © 2008 John Wiley & Sons, Ltd.