Multiple-step melting in two-dimensional hexatic liquid-crystal films

An unexpected three-stage melting transition has been observed in two-dimensional (2D) free-standing liquid-crystal films by in situ electron-diffraction and optical-reflectivity measurements. These data suggest the existence of two phases between the 2D solid and liquid: a hexatic phase and, at a higher temperature, an intermediate liquid phase with hexatic-like positional correlations ( approximately 40 angstroms) but no long-range orientational order. Previous high-resolution heat-capacity measurements have revealed a divergent-like anomaly at the hexatic-liquid transition that sharply contradicts the predictions of 2D melting theories. The observation of an intermediate isotropic phase may alter our understanding of 2D melting and lead to reconciliation between current experiments and theories.     

Melting of diamond at high pressure

Melting of diamond at high pressure and the properties of liquid carbon at pressures greater than 1 megabar were investigated with a first-principles molecular dynamics technique. The results indicate an increase of the diamond melting temperature with pressure, which is opposite to the behavior of silicon and germanium. This is contrary to long-held assumptions, but agrees with recent experiments, and has important implications for geology and astrophysics. As is the case for the solid phase of carbon at low temperature, which changes greatly with pressure from graphite to diamond, the structural and bonding properties of liquid carbon vary strongly with pressure.     

Phase-separated composite films for liquid crystal displays

A method of preparing liquid crystal devices by phase separation of liquid crystal from its solution in a prepolymer, which results in adjacent layers of liquid crystal and polymer, is described. Liquid crystals in these phase-separated composite films exhibit electro-optical properties not observed in devices prepared by conventional methods, polymer dispersion, or polymer-stabilization methods. Devices incorporating ferroelectric liquid crystals have gray scale and switch 100 times faster at low fields than conventional surface-stabilized devices. This method makes it possible to prepare devices with liquid crystal film thickness comparable to optical wavelengths.     

Melting of diamond

Radiation from a Q-switched YAG laser, focused on the (100) face of a single crystal diamond anvil in a high-pressure diamond cell, caused a portion of the diamond anvil face to melt. Potassium bromide mixed with graphite was under pressure between the anvils when melting occurred. The diamond surface melted at pressures greater than approximately 120 kilobars and graphitized at lower pressures. Evidence for the melting and graphitization of the diamond was obtained by optical and scanning electron microscopy.     

Near--Atomic Resolution Imaging of Ferroelectric Liquid Crystal Molecules on Graphite by STM

Near-atomic resolution images of a two-dimensional heteroepitaxial crystal composed of the relatively "functionally rich" chiral liquid crystal mesogen MDW 74 on graphite have been obtained by scanning tunneling microscopy (STM). This work is aimed at developing an improved understanding of the commercially crucial phenomenon of liquid crystal alignment by studying well-characterized surfaces. Herein is reported molecular-level characterization of the surface underlying a ferroelectric liquid crystal in situ, a requisite starting point for understanding the liquid crystal-solid interface at the molecular level. The results are also important in the context of developing a model for the molecular. origins of the contrast observed in STM images of organic monolayers on conductor surfaces. The data and analysis provide strong evidence that neither frontier orbital alone (highest occupied or lowest unoccupied molecular orbital) is sufficient to describe the observed tunneling efficiency.     

Control of structure and growth of polymorphic crystalline thin films of amphiphilic molecules on liquid surfaces

The spontaneous formation and coexistence of crystalline polymorphic trilayer domains in amphiphilic films at air-liquid interfaces is demonstrated by grazing incidence synchrotron x-ray diffraction. These polymorphic crystallites may serve as models for the early stages of crystal nucleation and growth, helping to elucidate the manner in which additives influence the progress of crystal nucleation, growth, and polymorphism and suggesting ways of selectively generating and controlling multilayers on liquid surfaces. Auxiliary molecules have been designed to selectively inhibit development of the polymorphs, leading primarily to a single phase monolayer.     

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.     

Structure and freezing of MgSiO3 liquid in Earth's lower mantle

First-principles molecular-dynamics simulations show that over the pressure regime of Earth's mantle the mean silicon-oxygen coordination number of magnesium metasilicate liquid changes nearly linearly from 4 to 6. The density contrast between liquid and crystal decreases by a factor of nearly 5 over the mantle pressure regime and is 4% at the core-mantle boundary. The ab initio melting curve, obtained by integration of the Clausius-Clapeyron equation, yields a melting temperature at the core-mantle boundary of 5400 +/- 600 kelvins.     

Experimental Evidence for a New Iron Phase and Implications for Earth's Core

Iron is known to occur in four different crystal structural forms. One of these, the densest form (epsilon phase, hexagonal close-packed) is considered to have formed Earth's core. Theoretical arguments based on available high-temperature and high-pressure iron data indicate the possibility of a fifth less dense iron phase forming the core. Study of iron phase transition conducted between pressures of 20 to 100 gigapascals and 1000 to 2200 Kelvin provides an experimental confirmation of the existence of this new phase. Thee epsilon iron phase transforms to this lower density phase before melting. The new phase may form a large part of Earth's core.     

Jumping nanodroplets

Flat gold nanostructures on inert substrates like glass or graphite were illuminated by single intensive laser pulses with fluences above the gold melting threshold. The liquid structures produced in this way are far from their equilibrium shape, and a dewetting process sets in. On a time scale of a few nanoseconds, the liquid contracted toward a sphere. During this contraction, the center of mass moved upward, which could lead to detachment of droplets from the surface due to inertia. The resulting velocities were on the order of 10 meters per second for droplets with radii in the range of 100 nanometers.     

Controlled deposition, soft landing, and glass formation in nanocluster-surface collisions

Molecular dynamics simulations have been used to investigate the dynamics and redistribution of energy during the impact of a nanocrystal with adsorbed liquid films. Although impact of a 32-molecule NaCl cluster on a solid surface at 3 kilometers per second leads to melting, disordering, fragmentation, and rebounding, the same size cluster colliding with a liquid neon film transfers its energy efficiently to the liquid for a controlled soft landing. Impact on a higher density film (argon) leads to rapid attenuation of the cluster velocity, accompanied by fast heating. Subsequent disordering, melting, and fast cooling by evaporation of argon quench the cluster to a glassy state. These results suggest a method for the controlled growth of nanophase materials.     

Biomimetic Pathways for Assembling Inorganic Thin Films

Living organisms construct various forms of laminated nanocomposites through directed nucleation and growth of inorganics at self-assembled organic templates at temperatures below 100°C and in aqueous solutions. Recent research has focused on the use of functionalized organic surfaces to form continuous thin films of single-phase ceramics. Continuous thin films of mesostructured silicates have also been formed on hydrophobic and hydrophilic surfaces through a two-step mechanism. First, under acidic conditions, surfactant micellar structures are self-assembled at the solid/liquid interface, and second, inorganic precursors condense to form an inorganic-organic nanocomposite. Epitaxial coordination of adsorbed surfactant tubules is observed on mica and graphite substrates, whereas a random arrangement is observed on amorphous silica. The ability to process ceramic-organic nanocomposite films by these methods provides new technological opportunities.     

Two-dimensional rare gas solids

Monolayers of rare gas atoms adsorbed onto the basal planes of graphite play the same prototype role in two dimensions that rare gas liquids and solids do in three dimensions. In recent experiments such novel phenomena as continuous melting, the lack of true crystallinity in two dimensions, orientationally ordered fluid phases, and melting from a solid to a reentrant fluid with decreasing temperature have been observed. Because the forces in these rare gas monolayers are simple and well understood, by studying them the investigator can examine a direct interface between experiment and first principles. In order to understand the phases and phase transitions that occur in such materials, it is necessary to consider the geometrical matching of the rare gas overlayer to the graphite substrate. It turns out that in two dimensions both the local and the long-distance behavior are important. These two-dimensional rare gas solids may be effectively probed with synchrotron x-ray techniques, and the results of a series of synchrotron x-ray scattering studies of these solids are presented.     

Domain structures in langmuir-blodgett films investigated by atomic force microscopy

Investigations of phase-separated Langmuir-Blodgett films by atomic force microscopy reveal that on a scale of 30 to 200 micrometers, these images resemble those observed by fluorescence microscopy. Fine structures (less than 1 micrometer) within the stearic acid domains were observed, which cannot be seen by conventional optical microscopic techniques. By applying the force modulation technique, it was found that the elastic properties of the domains in the liquid condensed phase and grains observed within the liquid expanded phase were comparable. Small soft residues in the domains could also be detected. The influence of trace amounts of a fluorescence dye on the micromorphology of monolayers could be detected on transferred films.     

A ferroelectric liquid crystal conglomerate composed of racemic molecules

We describe the design and synthesis of a ferroelectric liquid crystal composed of racemic molecules. The ferroelectric polarization results from spontaneous polar symmetry breaking in a fluid smectic. The ferroelectric phase is also chiral, resulting in the formation of a mixture of macroscopic domains of either handedness at the isotropic-to-liquid crystal phase transition. This smectic liquid crystal is thus a fluid conglomerate. Detailed investigation of the electrooptic and polarization current behavior within individual domains in liquid crystal cells shows the thermodynamically stable structure to be a uniformly tilted smectic bow-phase (banana phase), with all layer pairs homochiral and ferroelectric (SmC(S)P(F)).     

Carbon: A New Crystalline Phase

The electrical resistance of single crystal graphite shows a very sharp increase at above 150 kilobars, accompanied by a drifting upward with time. The behavior is typical of a first-order phase transition, and is irreversible. X-rays on the material after removal from the cell show lines of a new material with a structure which can be indexed as a cubic lattice with a unit cell edge of 5.545 angstroms. The density of the new phase is estimated at 2.80 grams per cubic centimeter.     

Self-organized discotic liquid crystals for high-efficiency organic photovoltaics

Self-organization of liquid crystalline and crystalline-conjugated materials has been used to create, directly from solution, thin films with structures optimized for use in photodiodes. The discotic liquid crystal hexa-peri-hexabenzocoronene was used in combination with a perylene dye to produce thin films with vertically segregated perylene and hexabenzocoronene, with large interfacial surface area. When incorporated into diode structures, these films show photovoltaic response with external quantum efficiencies of more than 34 percent near 490 nanometers. These efficiencies result from efficient photoinduced charge transfer between the hexabenzocoronene and perylene, as well as from effective transport of charges through vertically segregated perylene and hexabenzocoronene pi systems. This development demonstrates that complex structures can be engineered from novel materials by means of simple solution-processing steps and may enable inexpensive, high-performance, thin-film photovoltaic technology.     

Raoult's Law and the Melting Point Depression in Mesoscopic Systems

Data on the melting point depression in small indium or gold particles and in liquid water held between lipid bilayers indicate that these systems obey Raoult's law, with the surface atoms or molecules acting like solute particles in a dilute solution.     

Magnetic flux-line lattices and vortices in the copper oxide superconductors

A variety of recent experiments on both the static and the dynamic properties of vortices and flux-line lattices in the mixed state of the copper oxide superconductors are discussed. The experiments are of two basic types: (i) experiments that image the magnetic flux patterns either with magnetic decoration or neutrons and give information about static structures, and (ii) experiments that explore the dynamics of vortices either through the resistivity or other electrodynamic responses of the material. Results of these experiments argue in favor of the existence of a true phase transition in the high-field vortex state from a low-temperature superconducting vortex glass phase into a disordered high-temperature vortex fluid phase. The vortex glass phase transition model does a good job of explaining high-precision measurements of the dynamics at the transition. At low fields and temperatures, very long range hexatic order in the flux-line lattice is observed.     

A new allotropic form of carbon from the ries crater

A new allotropic form of carbon occurs in shock-fused graphite gneisses in the Ries Crater, Bavaria. The assemblage in which it occurs consists of hexagonal graphite, rutile, pseudobrookite, magnetite, nickeliferous pyrrhotite, and baddeleyite. Electron-probe analyses indicate that the new phase is pure carbon. It is opaque and much more strongly reflecting than hexagonal graphite. Measurement of x-ray diffraction powder patterns leads to cell dimensions a = 8.948 +/- 0.009, c = 14.078 +/- 0.017 angstroms, with a primitive hexagonal lattice.