Nanoscale Structure of the Oil-Water Interface.

X-ray reflectivity (XR) and atomistic molecular dynamics (MD) simulations, carried out to determine the structure of the oil-water interface, provide new insight into the simplest liquid-liquid interface. For several oils (hexane, dodecane, and hexadecane) the XR shows very good agreement with a monotonic interface-normal electron density profile (EDP) broadened only by capillary waves. Similar agreement is also found for an EDP including a sub-Å thick electron depletion layer separating the oil and the water. The XR and MD derived depletions are much smaller than reported for the interface between solid-supported hydrophobic monolayers and water.

Structure of n-Alkyltrichlorosilane Monolayers on Si(100)/SiO2.

The structure of n-alkyltrichlorosilane self-assembled monolayers (SAMs) of alkyl chain lengths n = 12, 14, 18, and 22 formed on the amorphous native oxide of silicon (100) has been investigated via angstrom-resolution surface X-ray scattering techniques, with particular focus on the proliferation of lateral order along the molecules' long axis. Grazing incidence diffraction shows that the monolayer is composed of hexagonally packed crystalline-like domains for n = 14, 18, and 22 with a lateral size of about 60 Å. However, Bragg rod analysis shows that ∼12 of the CH2 units are not included in the crystalline-like domains. We assign this, and the limited lateral crystallites' size, to strain induced by the size mismatch between the optimal chain-chain and headgroup-headgroup spacings. Analysis of X-ray reflectivity profiles for n = 12, 14, and 22 shows that the density profile used to successfully model n = 18 provides an excellent fit where the analysis-derived parameters provide complementary structural information to the grazing incidence results.

Pseudorotational epitaxy of self-assembled octadecyltrichlorosilane monolayers on sapphire (0001).

The structure of octadecyltrichlorosilane self-assembled monolayers (SAMs) on sapphire (0001) was studied by Å-resolution surface-specific x-ray scattering methods. The monolayer was found to consist of three sublayers where the outermost layer corresponds to vertically oriented, closely packed alkyl tails. Laterally, the monolayer is hexagonally packed and exhibits pseudorotational epitaxy to the sapphire, manifested by a broad scattering peak at zero relative azimuthal rotation, with long powderlike tails. The lattice mismatch of ∼ 1%-3% to the sapphire's and the different length scale introduced by the lateral Si-O-Si bonding prohibit positional epitaxy. However, the substrate induces an intriguing increase in the crystalline coherence length of the SAM's powderlike crystallites when rotationally aligned with the sapphire's lattice. The increase correlates well with the rotational dependence of the separation of corresponding substrate-monolayer lattice sites.

Stability of thin wetting films on chemically nanostructured surfaces.

The morphology and stability of thin volatile wetting films on model chemically patterned surfaces composed of periodic arrays of alternating completely and partially wettable nanostripes are investigated. The equilibrium film morphology is recorded as a function of undersaturation using noncontact atomic force microscopy. Films spanning the entire pattern are found to be stable only for thicknesses in excess of a critical value, h(c), whereas thinner films spontaneously dewet the partially wettable regions of the substrate. The critical thickness h(c) increases linearly with the width of the partially wettable stripes in good agreement with an interface displacement model derived from microscopic density functional theory. These results provide detailed insights into the dewetting of thin films driven by competing intermolecular forces.

Checkerboard self-patterning of an ionic liquid film on mercury.

Å-resolution studies of room temperature ionic liquid (RTIL) interfaces are scarce, in spite of their long-recognized importance for the science and many applications of RTILs. We present an Å-resolution x-ray study of a Langmuir film of an RTIL on mercury. At low (high) coverage [90 (50) Å2/molecule] a mono-(bi)layer of surface-parallel molecules is found. The molecules self-assemble in a lateral ionic checkerboard pattern, unlike the uniform-charge, alternate-ion layers of this RTIL at its bulk-solid interface. A 2D-smectic order is found, with molecules packed in parallel stripes, forming long-range order normal to, but none along, the stripes.

Unifying interfacial self-assembly and surface freezing.

X-ray investigations reveal that the monolayers formed at the bulk alkanol-sapphire interface are densely packed with the surface-normal molecules hydrogen bound to the sapphire. About 30-35 °C above the bulk, these monolayers both melt reversibly and partially desorb. This system exhibits balanced intermolecular and molecule-substrate interactions which are intermediate between self-assembled and surface-frozen monolayers, each dominated by one interaction. The phase behavior is rationalized within a thermodynamic model comprising interfacial interactions, elasticity, and entropic effects. Separating the substrate from the melt leaves the monolayer structurally intact.

Surface layering at the mercury-electrolyte interface.

X-ray reflectometry reveals atomic layering at a liquid-liquid interface--mercury in a 0.01 M NaF solution. The interface width exceeds capillary wave theory predictions and displays an anomalous dependence on the voltage applied across it, displaying a minimum positive of the potential of zero charge. The latter is explained by electrocapillary effects and an additional intrinsic broadening of the interface profile, tentatively assigned to polarization of the conduction electrons due to the electric field of the electrochemical double layer at the interface.

Wetting of nanopatterned grooved surfaces.

The wetting by perfluoromethylcyclohexane of a well-defined silicon grating with a channel width of 16 nm has been studied using transmission small angle x-ray scattering. Prefilling, capillary filling, and postfilling wetting regimes have been identified. A detailed comparison of the data with theory reveals the importance of long-ranged substrate-fluid and fluid-fluid interactions for determining the wetting behavior on these length scales, especially at the onset of capillary condensation and in the prefilling regime.

Dynamics and critical damping of capillary waves in an ionic liquid.

The dynamics of thermal capillary waves (CWs) on an ionic liquid's surface are studied at the transition from propagating to overdamped CWs by x-ray photon correlation spectroscopy. The analysis considers both homodyne and heterodyne contributions, and yields excellent full line-shape experiment-theory agreement for the structure factor. The CWs' Brillouin scattering becomes extinct at a critical temperature Tc JK approximately 10 K above Tc LL , the propagating modes' hydrodynamic limit, in agreement with linear response theory. Surprisingly, the same power law applies at both Tc. The results rule out the presence of a suggested surface dipole layer.

Wetting, mixing, and phase transitions in Langmuir-Gibbs films.

Millimolar bulk concentrations of the surfactant cetyltrimethylammonium bromide (CTAB) induce spreading of alkanes, H(CH(2))(n)H (denoted C(n)) 12< or =n< or =21, on the water surface, which is not otherwise wet by these alkanes. The novel Langmuir-Gibbs film (LGF) formed is a liquidlike monolayer comprising both alkanes and CTAB tails. Upon cooling, an ordering transition occurs, yielding a hexagonally packed, quasi-2D crystal. For 11< or =n< or =17 this surface-frozen LGF is a crystalline monolayer. For 18< or =n< or =21 the LGF is a bilayer with a crystalline, pure-alkane, upper monolayer, and a liquidlike lower monolayer. The phase diagram and film structure were determined by x-ray, ellipsometry, and surface tension measurements. A thermodynamic theory accounts quantitatively for the observations.

Alkyl-thiol Langmuir films on the surface of liquid mercury.

The coverage dependent phase behavior of monolayers of alkyl thiols (CH3(CH2)(n-1)SH, denoted as CnSH) on mercury was studied for chain lengths 9

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.

Surface freezing in binary alkane-alcohol mixtures.

Surface freezing was detected and studied in mixtures of alcohol and alkane molecules, using surface tensiometry and surface-specific x-ray scattering methods. Considering that surface freezing in pure alkanes forms an ordered monolayer and in alcohols it forms an ordered bilayer, the length mismatch repulsion was minimized by varying the carbon number of the alkane component around 2n, where n is the carbon number of the alcohol molecule. A solutionlike behavior was found for all mixtures, where the ideal liquid mixture phase-separates upon freezing both in the bulk and the surface. The solid exhibits a herringbone crystalline phase below an alkane mole fraction phi(t) approximately 0.8 and a rotator phase above it. The surface frozen film below phi(t) is an alkane monolayer exhibiting a next-nearest neighbor molecular tilt of a composition-dependent magnitude. Above phi(t), no diffraction peaks were observed. This could be explained by the intrinsically shorter-range order of the rotator phase and a possible proliferation of defects.

Crystalline phases of alkyl-thiol monolayers on liquid mercury.

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 A(2)/molecule from a rectangular packing of molecules tilted by 27 degrees 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.

Adsorbate-geometry specific subsurface relaxation in the CO/Pt(111) system.

A dramatic multilayer substrate relaxation is observed for the (square root 19 x square root 19)-13CO adlayer phase on a Pt(111) electrode by surface X-ray scattering. Within the (square root 19 x square root 19) unit cell, a vertical expansion of 0.28 A was determined for the Pt atoms under near-top-site CO molecules, whereas only 0.04 A was found under near-bridge-site CO molecules. The lateral displacements involve small rotations toward more symmetric bonding. Both the expansions and rotations extend into the bulk with a decay length of 1.8 Pt layers. This nonuniform layer expansion, hitherto unseen, appears to be a manifestation of the differential stress induced by CO adsorption at different sites.

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.

Surface and bulk interchange energy in binary mixtures of chain molecules.

The interchange (interaction) parameter, controlling the phase behaviour of a binary mixture, is determined for the bulk and the surface of binary mixtures of different types of chain molecules, using surface tensiometry and a mean-field theory. For all mixtures and concentrations studied an identical behaviour is observed at the surface, depending only on the square of the reduced chain length mismatch delta n/n, where delta n and dealta n are the difference in and average of the number of carbons of the two components.

Fatty acid Langmuir films on liquid mercury: X-ray and surface tension studies.

The structure and phase behavior of liquid-mercury-supported molecular films of fatty acids (CH3(CH2)n-2COOH, denoted CnOOH) were studied for molecular lengths 7 < or = n < or = 24, by surface tensiometry and X-ray methods. Two qualitatively different film structures were found, depending on coverage. For high coverage, the film consists of a monolayer of roughly surface-normal molecules, showing a pressure-dependent sequence of structures similar, though not identical, to that of the corresponding water-supported Langmuir films. At low coverage, phases consisting of surface-parallel molecules are found, not observed on the aqueous subphases employed to date. In this range, a two-dimensional (2D) gas followed by a single and, for 14 < or = n < or = 24, also by a double layer of surface-parallel molecules is found as coverage is increased. Depending on chain length, the flat-lying phases have a crystalline 2D-ordered, a smectic-like 1D-ordered, or a disordered in-plane structure consisting of molecular dimers. The structure and thermodynamics of the films are discussed.

The structure and phase diagram of Langmuir films of alcohols on mercury.

The coverage-dependent phase behavior of molecular films of alcohols (CH3(CH2)n-2CH2OH, denoted as CnOH) on mercury was studied for chain lengths 8 < or = n < or = 28, using surface tensiometry and surface specific X-ray methods. Phases with surface-normal-oriented molecules are found at high coverage, showing the CS, S, and LS phases found also on water. Phases comprising surface parallel molecules, which do not exist on water, are found here at low coverage. For the lowest coverage a two-dimensional gas phase is found, followed, upon increasing the coverage, by an n-dependent sequence of condensed phases of up to four layers of surface-parallel molecules before converting to the surface-normal phases. In contrast with the surface-normal phases, all of the surface-parallel phases are found to lack long-range order in the surface-parallel direction. Adsorption energies are derived from the phase diagram for the alkyl chain and the alcohol headgroup.