L. Tamam

The surface structure of concentrated aqueous salt solutions

The surface-normal electron density profile rhos(z) of concentrated aqueous salt solutions of RbBr, CsCl, LiBr, RbCl, and SrCl2 was determined by x-ray reflectivity (XR). For all but RbBr and SrCl2 rhos(z) increases monotonically with depth z from rhos(z)=0 in the vapor (z<0) to rhos(z)=rhob of the bulk (z>0) over a width of a few angstroms. The width is commensurate with the expected interface broadening by thermally excited capillary waves. Anomalous (resonant) XR of RbBr reveals a depletion at the surface of Br- ions to a depth of approximately 10 A. For SrCl2, the observed rhos(z)>rhob may imply a similar surface depletion of Cl- ions to a depth of a few angstorms. However, as the deviations of the XRs of RbBr and SrCl2 from those of the other solutions are small, the evidence for a different ion composition in the surface and the bulk is not strongly conclusive. Overall, these results contrast earlier theoretical and simulational results and nonstructural measurements, where significant surface layering of alternate, oppositely charged, ions is concluded.

Temperature dependence of the structure of Langmuir films of normal-alkanes on liquid mercury

The temperature dependent phase behavior of Langmuir films of n-alkanes [CH3(CH2)(n-2)CH3, denote Cn] on mercury was studied for chain lengths 19< or =n< or =22 and temperatures 15< or =T< or =44 degrees C, using surface tensiometry and surface x-ray diffraction methods. In contrast with Langmuir films on water, where molecules invariably orient roughly surface normal, alkanes on mercury are always oriented surface parallel and show no long-range in-plane order at any surface pressure. A gas and several condensed phases of single, double, and triple layers of lying-down molecules are found, depending on n and T. At high coverages, the alkanes studied here show transitions from a triple to a double to a single layer with increasing temperature. The transition temperature from a double to a single layer is found to be approximately 5 degrees C, lower than the bulk rotator-to-liquid melting temperature, while the transition from a triple to a double layer is about as much below the double-to-single layer transition. Both monolayer and bulk transition temperatures show a linear increase with n with identical slopes of approximately 4.5 degrees C/CH2 within the range of n values addressed here. It is suggested that the film and bulk transitions are both driven by a common cause: the proliferation of gauche defects in the chain with increasing temperature.

The structure and phase diagram of chiral alkyl-serine monolayers on mercury

The structure of liquid-mercury-supported Langmuir films (LFs) of chiral serine-modified fatty acid molecules was studied as a function of length, n = 8–22 carbons, temperature, T = 5–25 °C, and surface coverage, A ≈ 40–200 A2 per molecule, for both homochiral and heterochiral compounds. Using surface pressure π-area A isotherms and surface-specific synchrotron X-ray diffraction methods the phase diagram was determined in detail. No lateral order was found for phases comprising surface-parallel molecules, in contrast with unmodified fatty acid LFs on mercury. For phases comprising standing-up molecules, long range lateral order was found for n ≥ 12, but no order for n = 8. The molecules in the ordered phases are extended, and tilt rigidly by ∼40° from the surface normal. The homochiral LFs pack in an oblique, single-molecule, unit cell. The heterochiral LFs pack in a body-centered rectangular unit cell, containing two molecules. Unlike unmodified fatty acid LFs, the structure of the standing-up phase does not vary with n, T or A. The interactions underlying these characteristics, and the role of chirality, are discussed.

Langmuir Films of Chiral Molecules on Mercury

Homo- and heterochiral Langmuir films of a chiral derivative of stearic acid are studied in situ on the surface of liquid mercury as a function of surface coverage by surface tensiometry and surface-specific synchrotron X-ray diffraction and reflectivity. A transition from a phase of surface-parallel molecules to a phase of standing-up molecules is found. The former shows no surface-parallel long-range order. The standing-up phase of both homochiral and heterochiral compositions exhibit long-range order. However, the former has an oblique unit cell with parallel molecular planes, and the later has a centered rectangular unit cell with a herringbone molecular packing. For both cases, the standing-up molecules are tilted by 44 degrees from the surface normal and pack at a density of 19.5 A(2)/molecule in the plane normal to the molecular long axis. Important differences are found, and discussed, between this behavior and that of a Langmuir film of the nonchiral stearic acid on mercury.

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 cells 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.