Two-Dimensional Order in Mercury-Supported Langmuir Films of Fatty Diacids

The structure of mercury-supported Langmuir films of dicarboxylic acid molecules with 13 <= n <= 22 carbons is studied by X-ray methods and surface tensiometry. The molecules lie surface-parallel, forming mono-, bi-, or trilayers, depending on coverage. All films exhibit a full 2D order of the same single-molecule oblique unit cell. In particular, the distinct odd-even structure difference of 3D crystals of the same molecules is not observed. The unit cell's width and angle show a small systematic decrease with n, while the length increases commensurately with the molecular length. These results show the films to consist of closely packed, extended, polymer-like chains of diacid molecules, bound by their carboxyl end groups. Evidence is presented for the inclusion of a single mercury atom in the carboxyl-carboxyl bond. The possible conformation of this bond and implications of the parity-independent structure are discussed.