Crystalline phases of alkyl-thiol monolayers on liquid mercury

B. M. Ocko, H. Kraack, P. S. Pershan, E. Sloutskin, L. Tamam, M. Deutsch

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The structure of octadecanethiol monolyers on liquid Hg surfaces, measured with subangstrom resolution, evolves with increasing coverage from a laterally disordered phase of surface-parallel molecules to ordered rotator phases of surface-normal molecules. For the latter, an abrupt transition is found at 19 Å2/molecule from a rectangular packing of molecules tilted by 27° in the nearest-neighbor direction to a hexagonal unit cell of untilted molecules. The unit cell of the tilted phase is centered for the chains and noncentered for the headgroups. The thiol headgroups associate in pairs with a single Hg atom, and the bonds form long-range orientational order. The different order of thiols on Au(111) and on Hg highlights the subphase's role in determining the overlayer's structure.

Original languageEnglish
Article number017802
JournalPhysical Review Letters
Issue number1
StatePublished - 14 Jan 2005


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