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On the kinetics and thermodynamics of S-X (X = H, CH3, SCH3, COCH3, and CN) cleavage in the formation of self-assembled monolayers of alkylthiols on Au(111)

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Title On the kinetics and thermodynamics of S-X (X = H, CH3, SCH3, COCH3, and CN) cleavage in the formation of self-assembled monolayers of alkylthiols on Au(111)
 
Creator JACCOB, M
RAJARAMAN, G
TOTTI, F
 
Subject DFT
Thiols
Kinetics and the mechanism of adsorption
Gold surface
EFFECTIVE CORE POTENTIALS
ORGANIZED MOLECULAR ASSEMBLIES
DISSOCIATIVE ELECTRON-TRANSFER
SCANNING-TUNNELING-MICROSCOPY
N-ALKANETHIOL MONOLAYERS
ATOMIC-FORCE MICROSCOPY
GOLD SURFACES
DIALKYL SULFIDES
THIOL MONOLAYERS
STRUCTURAL-CHARACTERIZATION
 
Description Abounding potential technological applications is one of the many reasons why adsorption of aliphatic thiols on gold surface is a subject of intense research by many research groups. Understanding and exploring the nature of adsorbed species, the site of adsorption and the nature of interaction between adsorbed species and the gold surface using experimental and theoretical investigations is an active area of pursuit. However, despite a large number of investigations to understand the atomistic structures of thiols on Au(111), some of the basic issues are still unaddressed. For instance, there is still no clear information about the mechanism of adsorption of alkylthiol on gold surface. Furthermore, the reactivity and mechanism of adsorption of alkylthiol is likely to differ when gold adatoms and/or vacancies in the gold layers are considered. In this work, we have tackled these issues by computing the stationary states involved in the thiols adsorption in order to shed light on the kinetics aspects of adsorption process. In this respect, we have considered a variety of thiols into consideration such as methylthiol, dimethylsulfide, dimethyldisulfide, thioacetates, and thiocyanates. We have also considered the cleavage mechanism in the clean and the reconstructed surface scenario and the structure, energetics and spin densities have been computed using electronic structure calculations. For all the studied cases, an homolytic cleavage of CH3S-X (X = H, CH3, SCH3, CN, and COCH3) bond has been found to occur upon adsorption on the gold surface.
 
Publisher SPRINGER
 
Date 2014-10-16T12:49:08Z
2014-10-16T12:49:08Z
2012
 
Type Article
 
Identifier THEORETICAL CHEMISTRY ACCOUNTS, 131(3)
http://dx.doi.org/10.1007/s00214-012-1150-x
http://dspace.library.iitb.ac.in/jspui/handle/100/15588
 
Language en