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The electrochemical interface of Au(100) and 1-butyl-3-methyl-imidazolium hexafluorophosphate has been characterized by cyclic voltammetry, electrochemical impedance spectroscopy and in situ STM, especially in two distinct potential ranges. In the vicinity of the potential of zero total charge--the value of which has been determined by immersion experiments--charging of the double layer is rather slow, it appears as if the ions comprising the ionic liquid would slowly exchange each other at the surface. In the other, very negative region the ordering of the cations has been observed by STM.

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Five hexaalkylguanidinium-based ionic liquids have been synthesised, and based on their cyclic voltammograms the most suited one, N,N-dibutyl-N',N'-diethyl-N'',N''-dimethylguanidinium bis(trifluoromethylsulfonyl)imide, has been chosen for electrochemical studies. The surface interaction of this room-temperature ionic liquid with single crystalline gold surfaces (Au(100) and Au(111)) has been investigated using cyclic voltammetry, impedance spectroscopy and in situ scanning tunnelling microscopy (STM). The interfacial capacitance was found to be very low; STM measurements revealed the hex-reconstruction and herringbone reconstruction for Au(100) and for Au(111), respectively, at negative potentials; that is, at these potentials no hints for ad-structures of the cation could be found.

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