Mercury induced reorientation of alkanethiolates adsorbed on gold

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-(CH₂)₂₁-SH) were investigated by IR-vis sum frequency generation (SFG). Well-ordered monolayers and films with submonolayer coverage with a high number of gauche conformations were prepared on polycrystalline gold substrates. Exposure to a saturated mercury atmosphere induces a major reorganization of the adsorbate phase indicated by a decrease of the average cant angle. Additionally, well-ordered films show an increase of gauche defects upon amalgamation. In contrast, films with submonolayer coverage exhibit an improvement of molecular order. The experiments suggest that amalgamation flattens the corrugation potential of the substrate and yields a separation of the thiol layer into areas of low thiol density with highly disordered alkyl chains and of higher density than on gold with an orientation of the molecules similar to what is observed on silver substrates.