Dissolution kinetics of octadecanethiolate monolayers electro-adsorbed on Au(1 1 1)

Monolayers of octadecanethiolate on Au(1 1 1) surface were formed under electrochemical control. The influence of the formation time on the reductive desorption process was studied by cyclic voltammetry and chronoamperometry. When the formation time is increased, the reductive desorption peak observed on the voltammograms is significantly shifted in the negative direction, while the cathodic charge is only slightly affected. This behaviour is attributed to a higher degree of organisation of the monolayers for longer formation times, highlighting the role of defect sites in promoting the dissolution. A good agreement was found between our experimental chronoamperograms and theoretical models describing the dissolution process by a shrinkage mechanism. It is demonstrated that a reorganisation process takes place, consisting in the merging of small condensed domains into larger ones. This annealing phenomenon is time and potential dependent, the largest condensed domains being obtained for the longest formation times and least negative potentials. © 2008 Elsevier B.V. All rights reserved.

Adsorption of 2-mercaptobenzimidazole on a Au(1 1 1) electrode

The description of the monolayer formed at Au(1 1 1) by 2-mercaptobenzimidazole (MBI) under potential control has been based on electrochemical data (charge measurements) and spectroscopic information from the subtractively normalized interfacial Fourier transform infrared spectroscopy method (SNIFTIRS). From the quantitative analysis of the SNIFTIR spectra, a surface coverage Γ/Γmax was extracted for each sample potential. The evolution of the coverage with potential was in full agreement with the charge density curve. The shift of the pzc in the presence of MBI indicates that the adsorbed molecules have a nonzero component of the permanent dipole moment in the direction perpendicular to the electrode surface. Thanks to the high quality of the spectra, it was possible to determine the orientation of MBI molecules at the surface in the monolayer and submonolayer range. The angle between the C2-axis of the molecule and the direction normal to the surface is close to 64 ± 4° and its small change (<15°) with potential indicates that the orientation of the molecules is chiefly controlled by the chemical interaction between the sulphur atom and the gold surface. © 2005 Elsevier Ltd. All rights reserved.

Electrochemical and FTIR characterization of the self-assembled monolayer of 2-mercaptobenzimidazole on Au(1 1 1)

The behaviour of a self-assembled monolayer of 2-mercaptobenzimidazole (MBI) at the Au(111) electrode has been examined using cyclic voltammetry and in situ FTIR spectroscopy. The charge associated with the reductive desorption is pH independent while the oxidative partial redeposition charge increases when the pH is lowered. This is due to differences between the nature and the solubility of the MBI desorption product. In alkaline and neutral media MBI desorbs as the thiolate. In contrast, in acidic solutions the thiol is the desorbed product. Subtractively normalized interfacial reflection Fourier transform absorption spectroscopy (SNIFTIRS) has been applied to investigate the MBI monolayer in contact with aqueous solutions of different pH. The SNIFTIRS data are in agreement with the electrochemical results. Moreover, quantitative analysis of the IR data provided evidence that adsorbed MBI molecules assume a tilted orientation with an angle of 60±5° between the C2 axis of the molecule and the direction normal to the gold surface. © 2003 Elsevier B.V. All rights reserved.

Experimental and density functional theory study of the vibrational properties of 2-mercaptobenzimidazole in interaction with gold

The vibrational properties of the 2-mercaptobenzimidazole (MBI) molecule in interaction with gold were examined by a combined approach of FTIR measurements and density functional theory (DFT). A complete assignment of the 42 normal modes of MBI has been performed on the basis of DFT calculations at the B3PW91 level in complement to the Raman and FTIR spectra. Calculations demonstrated that, on the deprotonated MBI molecule, the negative charge is localized on the sulfur atom, favoring the formation of a gold-sulfur bond upon reaction of MBI with gold. This was confirmed by the very good agreement between the calculated spectrum and the experimental spectra of different gold-MBI compounds, indicating that the vibrational properties of adsorbed MBI are chiefly determined by the coordination through the sulfur atom. © 2006 American Chemical Society.