This work concerns the study of self-assembled monolayers (SAMs) on gold surfaces by molecular simulation. Electroactive SAMs formed by both ferrocenylalkanethiol and alkanethiol chains and SAMs of immobilized β-cyclodextrins that can form inclusion complexes at the interface were investigated. The objective of this study was to use molecular simulation to reproduce macroscopic properties that can be directly compared with experimental results. Molecular dynamics simulations are coupled to perturbation methods in order to calculate redox properties and thermodynamic properties of association. The comparison with experimental data allows us to validate simulation methodologies and forcefields and to consider simulation as a predictive tool for the study of new systems. Molecular dynamic also provides a rationalization of the macroscopic properties at the atomic level by a structural and energetic analysis of the processes involved in the reactions.
