Adsorption of probe molecules in pillared interlayered clays: experiment and computer simulation.

In this paper we investigate the adsorption of various probe molecules in order to characterize the porous structure of a series of pillared interlayered clays (PILC). To that aim, volumetric and microcalorimetric adsorption experiments were performed on various Zr PILC samples using nitrogen, toluene, and mesitylene as probe molecules. For one of the samples, neutron scattering experiments were also performed using toluene as adsorbate. Various structural models are proposed and tested by means of a comprehensive computer simulation study, using both geometric and percolation analysis in combination with Grand Canonical Monte Carlo simulations in order to model the volumetric and microcalorimetric isotherms. On the basis of this analysis, we propose a series of structural models that aim at accounting for the adsorption experimental behavior, and make possible a microscopic interpretation of the role played by the different interactions and steric effects in the adsorption processes in these rather complex disordered microporous systems.

Numerically efficient real space theory of scattering from colloidal crystals.

The production of high-quality colloidal crystals demands precise quantitative characterization of their nanostructures. While small-angle radiation scattering is the technique of choice, a procedure for a comprehensive quantitative modeling of the data is still pending. A novel theory based on the pertinent radial pair distribution which takes into account orientational, positional, stacking disorder and grain effects is developed here. We also show how the scattering length density of the particles can be estimated from the positions of minima in the form factor. The obtained results can be cast as sums of analytical functions over the distribution function and, as such, are suitable for easy (automatic) parallelization. On the experimental side, we report on a strong extinction effect coming from grazing incidence specular reflection that we have been able to model analytically.

Tracking the effects of rigidity percolation down to the liquid state: relaxational dynamics of binary chalcogen melts.

The stochastic dynamics of binary liquids with formula AxB1-x, x=0-0.4 is investigated by neutron spin-echo spectroscopy. These compositions comprise samples of varying chemical connectivity, ranging from twofold-coordinated liquid Se to higher average coordinated As2S3. The parameters giving the temperature dependence of the relaxation patterns show a quasilinear dependence on the average coordination number. The results thus extend the validity of the rigidity concept into the normal liquid state and emphasize the role played by the fine details of atomic bonding on the dynamics at 10 ps-1 ns scales.

Nature of the bound states of molecular hydrogen in carbon nanohorns.

The effects of confining molecular hydrogen within carbon nanohorns are studied via high-resolution quasielastic and inelastic neutron spectroscopies. Both sets of data are remarkably different from those obtained in bulk samples in the liquid and crystalline states. At temperatures where bulk hydrogen is liquid, the spectra of the confined sample show an elastic component indicating a significant proportion of immobile molecules as well as distinctly narrower quasielastic line widths and a strong distortion of the line shape of the para-->ortho rotational transition. The results show that hydrogen interacts far more strongly with such carbonous structures than it does to carbon nanotubes, suggesting that nanohorns and related nanostructures may offer significantly better prospects as lightweight media for hydrogen storage applications.

Evidence of the presence of opticlike collective modes in a liquid from neutron scattering experiments.

Inelastic neutron scattering data from liquid DF close to the melting point show, in addition to spectra comprising quasielastic and heavily damped acoustic motions, an intense, nondispersive band centered at about 27 meV along with a broader higher energy feature. Observation of the former band provides the first direct verification of the existence within the liquid state of collective opticlike excitations as predicted by molecular dynamics simulations. The latter corresponds to mainly reorientational motions assigned from mode eigenvector analysis carried out by computer simulations.

Unconventional density dependence of the stochastic dynamics in an organic liquid.

The density dependence of the diffusive rotational and center-of-mass dynamics of 2-methyl-pyridine is investigated by means of the concurrent use of quasielastic neutron scattering and molecular dynamics simulations. The dependence of both translation and rotational diffusion coefficients shows a distinctive change of slope with increasing density taking place about rho=0.975 g/cm3. Such a change in the dynamics can be related to observations made in other liquids composed of oblate-spheroidal particles.

How well do we know atomic motions of simple liquids?

Microscopic motions in molten potassium spanning three frequency decades are studied by neutron-scattering techniques. These comprise well-defined density oscillations and stochastic particle rearrangements and both are modeled on microscopic grounds. While vibratory motions are shown to share characteristics with those of their parent crystals, dynamic correlations between a diffusing particle and its neighbors can be accounted for only semiquantitatively.

Chemical isomerism as a key to explore free-energy landscapes in disordered matter.

The effects of a minor chemical modification on the microscopic structure of a material in its glass and crystal phases are investigated by the concurrent use of neutron diffraction and computer simulation. Significant changes in short-, intermediate-, and long-range order are found, resulting from the change in molecular structure. These differences are explainable by a shift in the balance between directional and excluded-volume interactions.

Hypothesis testing for the genetic background of quantitative traits.

The testing of Bayesian point null hypotheses on variance component models have resulted in a tough assigmment for which no clear and generally accepted method exists. In this work we present what we believe is a succeeding approach to such a task. It is based on a simple reparameterization of the model in terms of the total variance and the proportion of the additive genetic variance with respect to it, as well as on the explicit inclusion on the prior probability of a discrete component at origin. The reparameterization was used to bypass an arbitrariness related to the impropriety of uninformative priors onto unbounded variables while the discrete component was necessary to overcome the zero probability assigned to sets of null measure by the usual continuous variable models. The method was tested against computer simulations with appealing results.

Quantum effects on liquid dynamics as evidenced by the presence of well-defined collective excitations in liquid para-hydrogen

The origin of the well-defined collective excitations found in liquid para-H2 by recent experiments is investigated. The persistence of their relatively long lifetimes down to microscopic scales is well accounted for by calculations carried out by means of path-integral-centroid molecular dynamics. In contrast only overdamped excitations are found in calculations carried within the classical limit. The results provide fully quantitative evidence of quantum effects on the dynamics of a simple liquid.

Persistence of well-defined collective excitations in a molten transition metal

Well-defined microscopic collective excitations are found in liquid Ni at 1763 K by means of inelastic neutron scattering. Such excitations are supported by the liquid despite an anharmonic character of its thermodynamic functions. Consideration of the detailed shape of the interionic pair potential provides a way to understand why atomic motions at microscopic scales behave in a way much closer to the alkali metals than to the liquefied rare gases.