Structural Transition in a Fluid of Spheroids: A Low-Density Vestige of Jamming.

A thermodynamically equilibrated fluid of hard spheroids is a simple model of liquid matter. In this model, the coupling between the rotational degrees of freedom of the constituent particles and their translations may be switched off by a continuous deformation of a spheroid of aspect ratio t into a sphere (t=1). We demonstrate, by experiments, theory, and computer simulations, that dramatic nonanalytic changes in structure and thermodynamics of the fluids take place, as the coupling between rotations and translations is made to vanish. This nonanalyticity, reminiscent of a second-order liquid-liquid phase transition, is not a trivial consequence of the shape of an individual particle. Rather, free volume considerations relate the observed transition to a similar nonanalyticity at t=1 in structural properties of jammed granular ellipsoids. This observation suggests a deep connection to exist between the physics of jamming and the thermodynamics of simple fluids.

Critical onset of layering in sedimenting suspensions of nanoparticles.

We quantitatively study the critical onset of layering in suspensions of nanoparticles in a solvent, where an initially homogeneous suspension, subject to an effective gravity a in a centrifuge, spontaneously forms well-defined layers of constant particle density, so that the density changes in a staircaselike manner along the axis of gravity. This phenomenon is well known; yet, it has never been quantitatively studied under reproducible conditions: therefore, its physical mechanism remained controversial and the role of thermal diffusion in this phenomenon was never explored. We demonstrate that the number of layers forming in the sample exhibits a critical scaling as a function of a; a critical dependence on sample height and transverse temperature gradient is established as well. We reproduce our experiments by theoretical calculations, which attribute the layering to a diffusion-limited convective instability, fully elucidating the physical mechanism of layering.

Structure and interactions in fluids of prolate colloidal ellipsoids: comparison between experiment, theory, and simulation.

The microscopic structure of fluids of simple spheres is well known. However, the constituents of most real-life fluids are non-spherical, leading to a coupling between the rotational and translational degrees of freedom. The structure of simple dense fluids of spheroids - ellipsoids of revolution - was only recently determined by direct experimental techniques [A. P. Cohen, E. Janai, E. Mogilko, A. B. Schofield, and E. Sloutskin, Phys. Rev. Lett. 107, 238301 (2011)]. Using confocal microscopy, it was demonstrated that the structure of these simple fluids cannot be described by hard particle models based on the widely used Percus-Yevick approximation. In this paper, we describe a new protocol for determining the shape of the experimental spheroids, which allows us to expand our previous microscopy measurements of these fluids. To avoid the approximations in the theoretical approach, we have also used molecular dynamics simulations to reproduce the experimental radial distribution functions g(r) and estimate the contribution of charge effects to the interactions. Accounting for these charge effects within the Percus-Yevick framework leads to similar agreement with the experiment.

Fluid suspensions of colloidal ellipsoids: direct structural measurements.

A fluid of spheroids, ellipsoids of revolution, is among the simplest models of the disordered matter, where positional and rotational degrees of freedom of the constituent particles are coupled. However, while highly anisometric rods, and hard spheres, were intensively studied in the last decades, the structure of a fluid of spheroids is still unknown. We reconstruct the structure of a simple fluid of spheroids, employing direct confocal imaging of colloids, in three dimensions. The ratio t between the polar axis and the equatorial diameter for both our prolate and oblate spheroids is not far from unity, which gives rise to a delicate interplay between rotations and translations. Strikingly, the measured positional interparticle correlations are significantly stronger than theoretically predicted, indicating that further theoretical attention is required, to fully understand the coupling between translations and rotations in these fundamental fluids.

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.

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.

The surface structure of ionic liquids: comparing simulations with x-ray measurements.

The surface-normal electron density profile of an ionic liquid, [bmim][PF6], derived from x-ray reflectivity measurements, is compared with two independent molecular-dynamics simulations. It is shown that a meaningful comparison requires a detailed accounting for both thermal and nonthermal surface roughening effects. The former is due to thermally excited capillary waves, and the latter is due to the molecular zero-point motion and form. These quantities influence very significantly, but differently, the simulated and measured density profiles. Stripping off these effects from both types of profiles yields the intrinsic structure factor of the surface. The simulated intrinsic structure factors are found to deviate considerably from the measured one. The introduction of additional ad hoc surface roughness to the simulated profiles greatly reduces the deviation, however, no physical origin for this effect can be identified. The method employed in this study should prove useful for simulation-experiment comparisons of other liquid surfaces, provided they obey capillary-wave theory, as do almost all liquid surfaces studied to date by x-ray reflectivity.

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.

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.

Surface freezing in binary mixtures of chain molecules. I. Alkane mixtures.

X-ray surface scattering and surface tension measurements are used to study surface freezing in molten mixtures of alkanes. These binary mixtures consist of protonated and deuterated alkanes, as well as of alkanes of different lengths. As for pure alkanes, a crystalline monolayer is formed at the surface a few degrees above the bulk freezing temperature. The structure of the monolayer has been determined on an angstrom scale. A simple theoretical approach is used to account for the thermodynamical observations at the surface and in the bulk. The model is based on a competition between entropic mixing and a repulsive interaction due to chain-length mismatch. The surface and bulk liquid phases are treated as ideal mixtures, while the solid phases are treated as regular mixtures. The theory is found to account well for all the mixtures studied, both hydrogenated-hydrogenated and hydrogenated-deuterated. The repulsive interaction and its dependence on the chain lengths of the components are determined from fits to the measured data.

Surface freezing in binary mixtures of chain molecules. II. Dry and hydrated alcohol mixtures.

Surface freezing is studied in dry and hydrated alcohol mixtures by surface x-ray scattering and surface tension measurements. A crystalline bilayer is formed at the surface a few degrees above the bulk freezing temperature. The packing is hexagonal, with molecules aligned along the surface normal in all cases. The in-plane lattice constant reveals a qualitatively different behavior with composition for hydrated and dry mixtures. The simple theoretical approach used successfully for alkane and deuterated alkane mixtures accounts well also for the alcohol mixtures. The repulsive length-mismatch term opposing the mixing entropy term in the free energy of the mixtures is shown to have a universal behavior for all mixtures studied: protonated alkanes, deuterated alkanes, and dry and wet alcohols. This universality is somewhat counterintuitive in view of the different interactions (e.g., hydrogen bonding in alcohols) in the different mixtures.

Structure of a Langmuir film on a liquid metal surface.

The structure of organic monolayers on liquid surfaces depends sensitively on the details of the molecular interactions. The structure of a stearic acid film on a mercury surface was measured as a function of coverage with angstrom resolution. Unlike monolayers on water, the molecules were found here to undergo a transition from surface-parallel to surface-normal orientation with increasing coverage. At high coverage, two condensed hexatic phases of standing-up molecules were found. At low coverage, a two-dimensional (2D) gas phase and condensed single- and double-layered phases of flat-lying molecular dimers were revealed, exhibiting a 1D longitudinal positional order. This system should provide a broader tunability range for nanostructure construction than solid-supported self-assembled monolayers.

Demixing transition in a quasi-two-dimensional surface-frozen layer.

A thin/thick transition was observed by x-ray reflectivity in a surface-frozen crystalline bilayer on the surface of a molten binary mixture of long alcohols. This rare example of a solid-solid phase transition in a quasi-2D system is shown to result from an abrupt temperature-driven change in the layer's composition, kinetically enabled by the layer's ability to exchange molecules with the underlying 3D liquid bulk. Mean-field thermodynamics yields a Gibbs-adsorption-like expression which accounts very well for the transition.

Surface freezing in n-alkane solutions: the relation to bulk phases.

Surface freezing (SF) was investigated in tricosane-dodecane alkane solutions as a function of temperature (T) and molar concentration of tricosane (phi), using surface tension and synchrotron x-ray surface diffraction techniques. A crystalline SF monolayer, having a rotator R(II) structure, was found to exist for 35 degrees C