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Probing interfacial solvation of incipient self-assembled monolayers.

Poor solvation of alkylthiols in a water-rich interfacial environment is shown to induce a dispersion of energetically-distinct states above a critical value of the hydrocarbon chain length, which depends on the hydrophilicity of the terminal group. Switching between single and dispersed states can be achieved by an adequate choice of the solvent composition.