Molecular simulation studies of self-assembled monolayers of alkanethiols on Au(111)

A review is presented of this group's recent molecular simulation studies of self-assembled monolayers (SAMs) of alkanethiols on Au(111) surfaces. SAMs are very useful for the systematic alteration of the chemical and structural properties of a surface by varying chain length, tail group and composition. The scientific and technological importance of SAMs cannot be overestimated. The present work has been centred on studies of atomic scale surface properties of SAMs. First, configurational-bias Monte Carlo simulations were performed in both semigrand canonical and canonical ensembles to investigate the preferential adsorption and phase behaviour of mixed SAMs on Au(111) surfaces. Second, a novel hybrid molecular simulation technique was developed to simulate atomic force microscopy (AFM) over experimental timescales. The method combines a dynamic element model for the tip-cantilever system in AFM and a molecular dynamics relaxation approach for the sample. The hybrid simulation technique was applied to investigate atomic scale friction and adhesion properties of SAMs as a function of chain length. Third, dual-control-volume grand canonical molecular dynamics (DCV-GCMD) simulations were performed of transport diffusion of liquid water and methanol through a slit pore with both inner walls consisting of Au(111) surfaces covered by SAMs under a chemical potential gradient. Surface hydrophobicity was adjusted by varying the terminal group of CH3 (hydrophobic) or OH (hydrophilic) of the SAMs. Finally, ab initio quantum chemical calculations were performed on both clusters and periodic systems of methylthiols on Au(111) surfaces. Based on the ab initio results, an accurate force field capable of predicting c(4 x 2) superlattice structures over a wide range of temperatures for alkanethiols on Au(111) was developed. The extension of current work is discussed briefly.