Equilibrium structure and shape of Ag and Pt nanoparticles grown on silica surfaces: From experimental investigations to the determination of a metal-silica potential.

A combination of experimental and numerical investigations on metallic silver and platinum nanoparticles deposited on silica substrates is presented, with a focus on metal-substrate interactions. Experimentally, the nanoparticles, obtained by ultra-high vacuum atom deposition, are characterized by grazing-incidence small-angle x-ray scattering and high resolution transmission electronic microscopy to determine their structure and morphology and, in particular, their aspect ratio (height/diameter), which quantifies the metal-substrate interaction, from the as-grown to equilibrium state. Numerically, the interactions between the metal and the silica species are modeled with the Lennard-Jones (12, 6) potential, with two parameters for each metal and silica species. The geometric parameters were found in the literature, while the energetic parameters were determined from our experimental measurements of the aspect ratio. The parameters are as follows: σAg-O = 0.278 nm, σAg-Si = 0.329 nm, ɛAg-O = 75 meV, and ɛAg-Si = 13 meV for Ag-silica and σPt-O = 0.273 nm, σPt-Si = 0.324 nm, ɛPt-O = 110 meV, and ɛPt-Si = 18 meV for Pt-silica. The proposed Ag-silica potential reproduces quantitatively the unexpected experimental observation of the variation of the aspect ratio for Ag nanoparticles larger than 5 nm, which has been interpreted as a consequence of the silica roughness. The nanoparticle orientation, structure, and disorder are also considered. This metal-silica potential for Ag and Pt should be helpful for further studies on pure metals as well as their alloys.

Bulk supercooled water versus adsorbed films on silica surfaces: specific heat by Monte Carlo simulation.

Between 150 and 230.6 K, bulk supercooled water freezes upon cooling, and amorphous ice crystallizes upon heating: bulk water thus exists only in its stable ice form. To circumvent this problem, experiments are generally performed on water adsorbed in SiO2 based porous systems. In this work, we take advantage of Monte Carlo simulations to explore this metastable supercooled region inaccessible to experiments. Using three rigid, non-polarizable water models, namely SPC, TIP4P and TIP4P/2005, we investigate the isobaric specific heat capacity (Cp), between 100 and 300 K, of bulk water and water films of few monolayers adsorbed on different SiO2 surfaces: a smooth surface, a non-hydroxylated (0001) surface of quartz, and a fully hydroxylated (001) surface of cristobalite. As Cp is directly related to the entropy fluctuations and we focus on low temperatures, the convergence of the Monte Carlo simulations is a critical point of this work. Also, due to the small mass of the hydrogen atoms, quantum corrections are taken into account, and lead to an excellent agreement of the simulated and experimental Cp values at low temperature (100 K region). Altogether, we conclude that, in bulk, Cp is shown to exhibit a broad peak around 225 K for the SPC and TIP4P models, and around 250 K for the TIP4P/2005 model, in qualitative agreement with the experimentally observed features in Cp measurements. For interfacial water, in all cases, the broad Cp peak disappears. This result, at odds with experimental observations, suggests that disorder and hydrogen bonding at the interface (not yet taken into account) have a fundamental role in confined water transitions.

Final analysis and results of the Phase II SIMPLE dark matter search.

We report the final results of the Phase II SIMPLE measurements, comprising two run stages of 15 superheated droplet detectors each, with the second stage including an improved neutron shielding. The analyses include a refined signal analysis, and revised nucleation efficiency based on a reanalysis of previously reported monochromatic neutron irradiations. The combined results yield a contour minimum of σp=5.7×10(-3) pb at 35 GeV/c2 in the spin-dependent sector of weakly interacting massive particle (WIMP) proton interactions, the most restrictive to date for MW}≤60 GeV/c2 from a direct search experiment and overlapping, for the first time, with results previously obtained only indirectly. In the spin-independent sector, a minimum of 4.7×10(-6) pb at 35 GeV/c2 is achieved, with the exclusion contour challenging a significant part of the light mass WIMP region of current interest.

First results of the Phase II SIMPLE dark matter search.

We report results of a 14.1 kg d measurement with 15 superheated droplet detectors of total active mass 0.208 kg, comprising the first stage of a 30 kg d Phase II experiment. In combination with the results of the neutron-spin sensitive XENON10 experiment, these results yield a limit of |a(p)|<0.32 for M(W)=50 GeV/c² on the spin-dependent sector of weakly interacting massive particle-nucleus interactions with a 50% reduction in the previously allowed region of the phase space, formerly defined by XENON, KIMS, and PICASSO. In the spin-independent sector, a limit of 2.3×10⁻5 pb at M(W)=45 GeV/c² is obtained.

Effect of the reservoir size on gas adsorption in inhomogeneous porous media.

We study the influence of the relative size of the reservoir on the adsorption isotherms of a fluid in disordered or inhomogeneous mesoporous solids. We consider both an atomistic model of a fluid in a simple, yet structured pore, whose adsorption isotherms are computed by molecular simulation, and a coarse-grained model for adsorption in a disordered mesoporous material, studied by a density functional approach in a local mean-field approximation. In both cases, the fluid inside the porous solid exchanges matter with a reservoir of gas that is at the same temperature and chemical potential and whose relative size can be varied, and the control parameter is the total number of molecules present in the porous sample and in the reservoir. Varying the relative sizes of the reservoir and the sample within experimental range may change the shape of the hysteretic isotherms, leading to a 're-entrant' behavior compared to the grand-canonical isotherm when the latter displays a jump in density. We relate these phenomena to the organization of the metastable states that are accessible for the adsorbed fluid at a given chemical potential or density.

The simple SDD.

We describe the fabrication and characterisation of the SIMPLE superheated droplet detector, a 10 g active mass device of C(2)ClF(5) in 1-3% weight concentrations currently employed in a direct search for spin-dependent astroparticle dark matter candidates.

Confinement effect on thermodynamic and structural properties of water in hydrophilic mesoporous silica.

The adsorption of water on porous silica surfaces at 300 K, has been qualitatively reproduced by Grand Canonical Monte Carlo simulations (GCMC) without any adjustment of adsorbate/substrate potential parameter. The simulated adsorption isotherm and isosteric differential enthalpy of adsorption compare well to experimental data for Vycor, showing the ability of the model in describing hydrophilic properties of silica surfaces. The analysis of fluid structure in the mesoporous glass gives detailed insights into confinement and disorder effects on water adsorbed on the hydrophilic surface of a porous glass. It is shown that hydrophilic properties are not simply related to surface hydroxyl density but are also related to local structure of the silica surface.

First dark matter limits from a large-mass, low-background, superheated droplet detector.

We report on the fabrication aspects and calibration of the first large active mass ( approximately 15 g) modules of SIMPLE, a search for particle dark matter using superheated droplet detectors (SDDs). While still limited by the statistical uncertainty of the small data sample on hand, the first weeks of operation in the new underground laboratory of Rustrel-Pays d'Apt already provide a sensitivity to axially coupled weakly interacting massive particles (WIMPs) competitive with leading experiments, confirming SDDs as a convenient, low-cost alternative for WIMP detection.