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Role of solvent selectivity in the equilibrium surface composition of monolayers formed from a solution containing mixtures of organic thiols.

We have developed a simple model to quantify the effect of solvent selectivity on the surface composition of two-component self-assembled monolayers formed from solutions containing mixtures of organic thiols. The coarse-grained molecular model incorporates the relevant intermolecular interactions in the solution and monolayer to yield an expression for the free energy of monolayer formation. Minimization of the free energy results in a simple and analytically tractable expression for the monolayer composition as a function of solvent selectivity (defined as the difference in the Flory-type interaction parameters of the two organic thiols in the solution) and the degree of incompatibility between the adsorbate molecules. A comparison of our theory to experiments on the formation of two-component self-assembled monolayers from solution indicates that the coarse-grained molecular model captures the trends in the experimental data quite well.