Measurement of the charge number per adsorbed molecule and packing densities of self-assembled long-chain monolayers of thiols.

We have applied a recently developed method (Langmuir 2006, 22, 5509-5519) to determine charge numbers per adsorbed molecule and packing densities in self-assembled monolayers (SAMs) of octadecanethiol (C18SH), a representative long-chain thiol. Our method yields values of area per molecule that are physically reasonable, in contrast to the popular reductive desorption method, which gives molecular areas that are smaller than those determined by the van der Waals radii. In a nonadsorbing electrolyte, we were able to model the dependence of the charge number per adsorbed molecule on the electrode potential, taking into account that the desorption process is a substitution reaction between the solvent and the adsorbate. We have also shown that the charge number per adsorbed thiol is affected by the specific adsorption of the anion of the electrolyte. In the latter case, the thiol competes for adsorption sites at the surface not only with water but also with the anion of the electrolyte, and this competition has an effect on the measured charge number.