Halide electroadsorption on single crystal surfaces

The structure and phase behavior of halides have been investigated on single crystals of Ag and Au using synchrotron x-ray scattering techniques. The adlayer coverages are potential dependent. For all halides studied the authors found that with increasing potential, at a critical potential, a disordered adlayer transforms into an ordered structure. Often these ordered phases are incommensurate and exhibit potential-dependent lateral separations (electrocompression). The authors have analyzed the electrocompression in terms of a model which includes lateral interactions and partial charge. A continuous compression is not observed for Br on Ag(100). Rather, they find that the adsorption is site-specific (lattice gas) in both the ordered and disordered phases. The coverage increases with increasing potential and at a critical potential the disordered phase transforms to a well-ordered commensurate structure

Surface crystallization in normal-alkanes and alcohols

A new, rare surface freezing, phenomenon is observed in molten normal-alkanes and their derivatives (alcohols, thiols, etc.). X-ray and surface tension measurements show the formation of a crystalline monolayer on the surface of the liquid alkane at temperatures up to 3 C above the bulk solidification temperature, T{sub f}. For alcohols, a single bilayer is formed. In both cases, the molecules in the layer are hexagonally packed and oriented normal to the surface for short chain lengths, and tilted for long ones. In both cases the single layer persists down to T{sub f}. In terms of wetting theory, this constitutes a very limited partial wetting of the liquid surface by the crystalline layer. The new surface phase is obtained only for chain lengths 14 < n {le} 50 in alkanes, and 16 < n < 30 in alcohols. The measurements are satisfactorily accounted for within a simple theory based on surface energy considerations

Ab initio calculations for bromine adlayers on the Ag(100) and Au(100) surfaces: the c(2x2) structure

Ab initio total-energy density-functional methods with supercell models have been employed to calculate the c(2x2) structure of the Br-adsorbed Ag(100) and Au(100) surfaces. The atomic geometries of the surfaces and the preferred bonding sites of the bromine have been determined. The bonding character of bromine with the substrates has also been studied by analyzing the electronic density of states and the charge transfer. The calculations show that while the four-fold hollow-site configuration is more stable than the two-fold bridge-site topology on the Ag(100) surface, bromine prefers the bridge site on the Au(100) surface. The one-fold on-top configuration is the least stable configuration on both surfaces. It is also observed that the second layer of the Ag substrate undergoes a small buckling as a consequence of the adsorption of Br. Our results provide a theoretical explanation for the experimental observations that the adsorption of bromine on the Ag(100) and Au(100) surfaces results in different bonding configurations.Comment: 10 pages, 4 figure, 5 tables, Phys. Rev. B, in pres

Microscopic View on Short-Range Wetting at the Free Surface of the Binary Metallic Liquid Gallium-Bismuth: An X-ray Reflectivity and Square Gradient Theory Study

We present an x-ray reflectivity study of wetting at the free surface of the binary liquid metal gallium-bismuth (Ga-Bi) in the region where the bulk phase separates into Bi-rich and Ga-rich liquid phases. The measurements reveal the evolution of the microscopic structure of wetting films of the Bi-rich, low-surface-tension phase along different paths in the bulk phase diagram. A balance between the surface potential preferring the Bi-rich phase and the gravitational potential which favors the Ga-rich phase at the surface pins the interface of the two demixed liquid metallic phases close to the free surface. This enables us to resolve it on an Angstrom level and to apply a mean-field, square gradient model extended by thermally activated capillary waves as dominant thermal fluctuations. The sole free parameter of the gradient model, i.e. the so-called influence parameter, $\kappa$, is determined from our measurements. Relying on a calculation of the liquid/liquid interfacial tension that makes it possible to distinguish between intrinsic and capillary wave contributions to the interfacial structure we estimate that fluctuations affect the observed short-range, complete wetting phenomena only marginally. A critical wetting transition that should be sensitive to thermal fluctuations seems to be absent in this binary metallic alloy.Comment: RevTex4, twocolumn, 15 pages, 10 figure

Surface layering of liquids: The role of surface tension

Recent measurements show that the free surfaces of liquid metals and alloys are always layered, regardless of composition and surface tension; a result supported by three decades of simulations and theory. Recent theoretical work claims, however, that at low enough temperatures the free surfaces of all liquids should become layered, unless preempted by bulk freezing. Using x-ray reflectivity and diffuse scattering measurements we show that there is no observable surface-induced layering in water at T=298 K, thus highlighting a fundamental difference between dielectric and metallic liquids. The implications of this result for the question in the title are discussed.Comment: 5 pages, 4 figures, to appear in Phys. Rev. B. 69 (2004

Hydrogen-bonded Silica Gels Dispersed in a Smectic Liquid Crystal: A Random Field XY System

The effect on the nematic to smectic-A transition in octylcyanobiphenyl (8CB) due to dispersions of hydrogen-bonded silica (aerosil) particles is characterized with high-resolution x-ray scattering. The particles form weak gels in 8CB creating a quenched disorder that replaces the transition with the growth of short range smectic correlations. The correlations include thermal critical fluctuations that dominate at high temperatures and a second contribution that quantitatively matches the static fluctuations of a random field system and becomes important at low temperatures.Comment: 10 pages, 4 postscript figures as separate file

Smectic ordering in liquid crystal - aerosil dispersions I. X-ray scattering

Comprehensive x-ray scattering studies have characterized the smectic ordering of octylcyanobiphenyl (8CB) confined in the hydrogen-bonded silica gels formed by aerosil dispersions. For all densities of aerosil and all measurement temperatures, the correlations remain short range, demonstrating that the disorder imposed by the gels destroys the nematic (N) to smectic-A (SmA) transition. The smectic correlation function contains two distinct contributions. The first has a form identical to that describing the critical thermal fluctuations in pure 8CB near the N-SmA transition, and this term displays a temperature dependence at high temperatures similar to that of the pure liquid crystal. The second term, which is negligible at high temperatures but dominates at low temperatures, has a shape given by the thermal term squared and describes the static fluctuations due to random fields induced by confinement in the gel. The correlation lengths appearing in the thermal and disorder terms are the same and show strong variation with gel density at low temperatures. The temperature dependence of the amplitude of the static fluctuations further suggests that nematic susceptibility become suppressed with increasing quenched disorder. The results overall are well described by a mapping of the liquid crystal-aerosil system into a three dimensional XY model in a random field with disorder strength varying linearly with the aerosil density.Comment: 14 pages, 13 figure

Atomic layering at the liquid silicon surface: a first- principles simulation

We simulate the liquid silicon surface with first-principles molecular dynamics in a slab geometry. We find that the atom-density profile presents a pronounced layering, similar to those observed in low-temperature liquid metals like Ga and Hg. The depth-dependent pair correlation function shows that the effect originates from directional bonding of Si atoms at the surface, and propagates into the bulk. The layering has no major effects in the electronic and dynamical properties of the system, that are very similar to those of bulk liquid Si. To our knowledge, this is the first study of a liquid surface by first-principles molecular dynamics.Comment: 4 pages, 4 figures, submitted to PR

X-ray reflectivity and surface roughness

Since the advent of high brightness synchrotron radiation sources there has been a phenomenal growth in the use of x-rays as a probe of surface structure. The technique of x-ray reflectivity is particularly relevant to electrochemists since it is capable of probing the structure normal to an electrode surface in situ. In this paper the theoretical framework for x-ray reflectivity is reviewed and the results from previous non-electrochemistry measurements are summarized. These measurements are from the liquid/air interface (CCl/sub 4/), the metal crystal vacuum interface (Au(100)), and from the liquid/solid interface(liquid crystal/silicon). 34 refs., 5 figs

Electrochemically induced reconstruction of the Au(001) surface: An x-ray scattering study

In-situ x-ray specular reflectivity and glancing incident angle x-ray diffraction measurements have been performed in the Au(001) surface in two solutions under potential control in an electrochemical cell. In both the 0.01 M HCl0{sub 4} and 0.01 M KBr solutions a (5 {times} 20)'' reconstruction is formed at sufficient negative potentials. The reconstruction is similar to that obtained for the clean surface in vacuum