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We present high-resolution optical birefringence measurements upon sequentialfilling of an array of parallel-aligned nanochannels (14~nm mean diameter) withrod-like (acetonitrile) and disc-like (hexafluorobenzene) molecules. We willdemonstrate that such birefringence isotherms, when performed simultaneouslywith optically isotropic and index-matched counterparts (neopentane andhexafluoromethane), allow one to characterize the orientational state of theconfined liquids with a high accuracy as a function of pore filling. The porecondensates are almost bulk-like, optically isotropic liquids. For bothanisotropic species we find, however, a weak orientational order (of a fewpercent at maximum) upon film-condensation in the monolithic mesoporousmembrane. It occurs upon formation of the second and third adsorbed layer,only, and vanishes gradually upon onset of capillary condensation. Presumably,it originates in the breaking of the full rotational symmetry of theinteraction potential at the cylindrical, free liquid-vapor interface in thefilm-condensed state rather than at the silica-liquid interface. Thisconclusion is corroborated by comparisons of our experimental results withmolecular dynamics simulations reported in the literature.

physical review. b, condensed matter and materials physics

Orientational Order in Liquids upon Condensation in Nanochannels: An  Optical Birefringence Study on Rodlike and Disclike Molecules in Monolithic  Mesoporous Silica