Surface Induced Order in Liquid Metals and Binary Alloys

Measurements of the surface x-ray scattering from several pure liquid metals (Hg, Ga, and In) and from three alloys (Ga-Bi, Bi-In, and K-Na) with different heteroatomic chemical interactions in the bulk phase are reviewed. Surface-induced layering is found for each elemental liquid metal. The surface structure of the K-Na alloy resembles that of an elemental liquid metal. Bi-In displays pair formation at the surface. Surface segregation and a wetting film are found for Ga-Bi.Comment: 10 pages, 3 fig, published in Journal of Physics: Condensed Matte

Surface Structure of Liquid Metals and the Effect of Capillary Waves: X-ray Studies on Liquid Indium

We report x-ray reflectivity (XR) and small angle off-specular diffuse scattering (DS) measurements from the surface of liquid Indium close to its melting point of $156^\circ$C. From the XR measurements we extract the surface structure factor convolved with fluctuations in the height of the liquid surface. We present a model to describe DS that takes into account the surface structure factor, thermally excited capillary waves and the experimental resolution. The experimentally determined DS follows this model with no adjustable parameters, allowing the surface structure factor to be deconvolved from the thermally excited height fluctuations. The resulting local electron density profile displays exponentially decaying surface induced layering similar to that previously reported for Ga and Hg. We compare the details of the local electron density profiles of liquid In, which is a nearly free electron metal, and liquid Ga, which is considerably more covalent and shows directional bonding in the melt. The oscillatory density profiles have comparable amplitudes in both metals, but surface layering decays over a length scale of $3.5\pm 0.6$ \AA for In and $5.5\pm 0.4$ \AA for Ga. Upon controlled exposure to oxygen, no oxide monolayer is formed on the liquid In surface, unlike the passivating film formed on liquid Gallium.Comment: 9 pages, 5 figures; submitted to Phys. Rev.

Absence of molecular mobility on nano-second time scales in amorphous ice phases

High-resolution neutron backscattering techniques are exploited to study the elastic and quasi-elastic response of the high-density amorphous (HDA), the low-density amorphous (LDA) and the crystalline ice Ic upon temperature changes. Within the temperature ranges of their structural stability (HDA at T > 80 K, LDA at T > 135 K, ice Ic at T < 200 K) the Debye-Waller factors and mean-square displacements characterise all states as harmonic solids. During the transformations HDA->LDA (T ~ 100 K), LDA->Ic (T ~ 150K) and the supposed glass transition with Tg ~ 135 K no relaxation processes can be detected on a time scale t < 4 ns. It can be concluded from coherent scattering measurements (D_2O) that LDA starts to recrystallise into ice Ic at T ~ 135 K, i.e. at the supposed Tg. In the framework of the Debye model of harmonic solids HDA reveals the highest Debye temperature among the studied ice phases, which is in full agreement with the lowest Debye level in the generalised density of states derived from time-of-flight neutron scattering experiments. The elastic results at low T indicate the presence of an excess of modes in HDA, which do not obey the Bose statistics

Ab initio van der Waals interactions in simulations of water alter structure from mainly tetrahedral to high-density-like

The structure of liquid water at ambient conditions is studied in ab initio molecular dynamics simulations using van der Waals (vdW) density-functional theory, i.e. using the new exchange-correlation functionals optPBE-vdW and vdW-DF2. Inclusion of the more isotropic vdW interactions counteracts highly directional hydrogen-bonds, which are enhanced by standard functionals. This brings about a softening of the microscopic structure of water, as seen from the broadening of angular distribution functions and, in particular, from the much lower and broader first peak in the oxygen-oxygen pair-correlation function (PCF), indicating loss of structure in the outer solvation shells. In combination with softer non-local correlation terms, as in the new parameterization of vdW-DF, inclusion of vdW interactions is shown to shift the balance of resulting structures from open tetrahedral to more close-packed. The resulting O-O PCF shows some resemblance with experiment for high-density water (A. K. Soper and M. A. Ricci, Phys. Rev. Lett., 84:2881, 2000), but not directly with experiment for ambient water. However, an O-O PCF consisting of a linear combination of 70% from vdW-DF2 and 30% from experiment on low-density liquid water reproduces near-quantitatively the experimental O-O PCF for ambient water, indicating consistency with a two-liquid model with fluctuations between high- and low-density regions

Thermodynamics and structure of self-assembled networks

We study a generic model of self-assembling chains which can branch and form networks with branching points (junctions) of arbitrary functionality. The physical realizations include physical gels, wormlike micells, dipolar fluids and microemulsions. The model maps the partition function of a solution of branched, self-assembling, mutually avoiding clusters onto that of a Heisenberg magnet in the mathematical limit of zero spin components. The model is solved in the mean field approximation. It is found that despite the absence of any specific interaction between the chains, the entropy of the junctions induces an effective attraction between the monomers, which in the case of three-fold junctions leads to a first order reentrant phase separation between a dilute phase consisting mainly of single chains, and a dense network, or two network phases. Independent of the phase separation, we predict the percolation (connectivity) transition at which an infinite network is formed that partially overlaps with the first-order transition. The percolation transition is a continuous, non thermodynamic transition that describes a change in the topology of the system. Our treatment which predicts both the thermodynamic phase equilibria as well as the spatial correlations in the system allows us to treat both the phase separation and the percolation threshold within the same framework. The density-density correlation correlation has a usual Ornstein-Zernicke form at low monomer densities. At higher densities, a peak emerges in the structure factor, signifying an onset of medium-range order in the system. Implications of the results for different physical systems are discussed.Comment: Submitted to Phys. Rev.

Transitions between Inherent Structures in Water

The energy landscape approach has been useful to help understand the dynamic properties of supercooled liquids and the connection between these properties and thermodynamics. The analysis in numerical models of the inherent structure (IS) trajectories -- the set of local minima visited by the liquid -- offers the possibility of filtering out the vibrational component of the motion of the system on the potential energy surface and thereby resolving the slow structural component more efficiently. Here we report an analysis of an IS trajectory for a widely-studied water model, focusing on the changes in hydrogen bond connectivity that give rise to many IS separated by relatively small energy barriers. We find that while the system \emph{travels} through these IS, the structure of the bond network continuously modifies, exchanging linear bonds for bifurcated bonds and usually reversing the exchange to return to nearly the same initial configuration. For the 216 molecule system we investigate, the time scale of these transitions is as small as the simulation time scale ($\approx 1$ fs). Hence for water, the transitions between each of these IS is relatively small and eventual relaxation of the system occurs only by many of these transitions. We find that during IS changes, the molecules with the greatest displacements move in small ``clusters'' of 1-10 molecules with displacements of $\approx 0.02-0.2$ nm, not unlike simpler liquids. However, for water these clusters appear to be somewhat more branched than the linear ``string-like'' clusters formed in a supercooled Lennar d-Jones system found by Glotzer and her collaborators.Comment: accepted in PR

Everyday legitimacy and international administration: global governance and local legitimacy in Kosovo

International administrations are a very specific form of statebuilding. This paper examines the limits illustrated by the experience in Kosovo. Here, the international administration faced the same requirements of any legitimate, Liberal government, but without the checks and balances normally associated with Liberal governance. Thus, the international administration was granted full authority and the power thereby associated, but without the legitimacy upon which the Liberal social contract rests. The state-building agenda put forth came to be seen as more exogenous, reinforcing the delegitimization process. This paper will specifically address the influence of the Weberian approach to legitimacy on the statebuilding literature, as well as its limits. It will then propose other possible avenues for statebuilding, more in line with a wider understanding of legitimacy and intervention

Rapid and Accurate Prediction and Scoring of Water Molecules in Protein Binding Sites

Water plays a critical role in ligand-protein interactions. However, it is still challenging to predict accurately not only where water molecules prefer to bind, but also which of those water molecules might be displaceable. The latter is often seen as a route to optimizing affinity of potential drug candidates. Using a protocol we call WaterDock, we show that the freely available AutoDock Vina tool can be used to predict accurately the binding sites of water molecules. WaterDock was validated using data from X-ray crystallography, neutron diffraction and molecular dynamics simulations and correctly predicted 97% of the water molecules in the test set. In addition, we combined data-mining, heuristic and machine learning techniques to develop probabilistic water molecule classifiers. When applied to WaterDock predictions in the Astex Diverse Set of protein ligand complexes, we could identify whether a water molecule was conserved or displaced to an accuracy of 75%. A second model predicted whether water molecules were displaced by polar groups or by non-polar groups to an accuracy of 80%. These results should prove useful for anyone wishing to undertake rational design of new compounds where the displacement of water molecules is being considered as a route to improved affinity