Temperature Dependence of the Optical Response of Small Sodium Clusters

We present an analysis of the temperature dependence of the optical response of small sodium clusters in a temperature range bracketing the melting phase transition. When the temperature increases, the mean excitation energy undergoes a red shift and the plasmon is significantly broadened, in agreement with recent experimental data. We show that the single--particle levels acquire a prominent width and the HOMO--LUMO gap as well as the width of the occupied band are reduced due to large thermal cluster size and shape fluctuations. This results in a sharp increase of the static polarizability with temperature.Comment: 9 pages, Revtex, 3 uuencoded postscript figure

Mesophases in Nearly 2D Room-Temperature Ionic Liquids

Computer simulations of (i) a [C12mim][Tf2N] film of nanometric thickness squeezed at kbar pressure by a piecewise parabolic confining potential reveal a mesoscopic in-plane density and composition modulation reminiscent of mesophases seen in 3D samples of the same room-temperature ionic liquid (RTIL). Near 2D confinement, enforced by a high normal load, relatively long aliphatic chains are strictly required for the mesophase formation, as confirmed by computations for two related systems made of (ii) the same [C12mim][Tf2N] adsorbed at a neutral solid surface and (iii) a shorter-chain RTIL ([C4mim][Tf2N]) trapped in the potential well of part i. No in-plane modulation is seen for ii and iii. In case ii, the optimal arrangement of charge and neutral tails is achieved by layering parallel to the surface, while, in case iii, weaker dispersion and packing interactions are unable to bring aliphatic tails together into mesoscopic islands, against overwhelming entropy and Coulomb forces. The onset of in-plane mesophases could greatly affect the properties of long-chain RTILs used as lubricants.Comment: 24 pages 10 figure

Squeezing lubrication films : layering transition for curved solid surfaces with long-range elasticity

The properties of an atomic lubricant confined between two approaching solids are investigated by a model that accounts for the curvature and elastic properties of the solid surfaces. Well defined atomic layers develop in the lubricant film when the width of the film is of the order of a few atomic diameters. An external squeezing-pressure induces discontinuous, thermally activated changes in the number n of lubricant layers. The precise mechanism for these layering transitions depends on n, and on the lubricant-surface pinning barriers. Thus, in the absence of sliding, unpinned or weakly pinned incommensurate lubricant layers give rise to fast and complete layering transitions. Strongly pinned incommensurate and commensurate layers give rise to sluggish and incomplete transformations, resulting in trapped islands. In particular, for commensurate layers it is often not possible to squeeze out the last few lubricant layers. However, lateral sliding of the two solid surfaces breaks down the pinned structures, greatly enhancing the rate of the layering transitions. In the case of sliding, an important parameter is the barrier for sliding one lubricant layer with respect to the others. When this barrier is larger than the lubricant-surface pinning barrier, the lubricant film tends to move like a rigid body with respect to the solid surface. In the opposite case, slip events may occur both within the lubricant film and at the lubricant-solid interface, making the squeeze-out process much more complex. In some of the simulations we observe an intermediate phase, forming immediately before the layering transition. This transient structure has a lower 2D density than the initial phase, and allows the system to release elastic energy, which is the driving force for the phase transformation. (C) 2000 American Institute of Physics. [S0021-9606(00)70421-1]

Thermoresponsive Ionic Liquid/Water Mixtures: From Nanostructuring to Phase Separation

The thermodynamics, structures, and applications of thermoresponsive systems, consisting primarily of water solutions of organic salts, are reviewed. The focus is on organic salts of low melting temperatures, belonging to the ionic liquid (IL) family. The thermo-responsiveness is represented by a temperature driven transition between a homogeneous liquid state and a biphasic state, comprising an IL-rich phase and a solvent-rich phase, divided by a relatively sharp interface. Demixing occurs either with decreasing temperatures, developing from an upper critical solution temperature (UCST), or, less often, with increasing temperatures, arising from a lower critical solution temperature (LCST). In the former case, the enthalpy and entropy of mixing are both positive, and enthalpy prevails at low T. In the latter case, the enthalpy and entropy of mixing are both negative, and entropy drives the demixing with increasing T. Experiments and computer simulations highlight the contiguity of these phase separations with the nanoscale inhomogeneity (nanostructuring), displayed by several ILs and IL solutions. Current applications in extraction, separation, and catalysis are briefly reviewed. Moreover, future applications in forward osmosis desalination, low-enthalpy thermal storage, and water harvesting from the atmosphere are discussed in more detail

3D AMR hydrosimulations of a compact source scenario for the Galactic Centre cloud G2

The nature of the gaseous and dusty cloud G2 in the Galactic Centre is still under debate. We present three-dimensional hydrodynamical adaptive mesh refinement (AMR) simulations of G2, modeled as an outflow from a "compact source" moving on the observed orbit. The construction of mock position-velocity (PV) diagrams enables a direct comparison with observations and allow us to conclude that the observational properties of the gaseous component of G2 could be matched by a massive ($\dot{M}_\mathrm{w}=5\times 10^{-7} \;M_{\odot} \mathrm{yr^{-1}}$) and slow ($50 \;\mathrm{km \;s^{-1}}$) outflow, as observed for T Tauri stars. In order for this to be true, only the material at larger ($>100 \;\mathrm{AU}$) distances from the source must be actually emitting, otherwise G2 would appear too compact compared to the observed PV diagrams. On the other hand, the presence of a central dusty source might be able to explain the compactness of G2's dust component. In the present scenario, 5-10 years after pericentre the compact source should decouple from the previously ejected material, due to the hydrodynamic interaction of the latter with the surrounding hot and dense atmosphere. In this case, a new outflow should form, ahead of the previous one, which would be the smoking gun evidence for an outflow scenario.Comment: resubmitted to MNRAS after referee report, 16 pages, 11 figure

Seasonal Occurrence and Distribution on Grapevine Roots of Eurhizococcus brasiliensis (Wille) (Hemiptera: Margarodidae) in Brazil

The ground pearl, Eurhizococcus brasiliensis (Wille) (Hemiptera: Margarodidae), is the most importantgrapevine pest in Brazil. Its seasonal occurrence and distribution on the roots of the different developmentstages were determined to allow better monitoring of this insect and better targeting of its vulnerable lifestages. Yellow cysts (after the first nymphal moult) showed the lowest density in October, followed by agradual increase towards August. White cysts (cysts with enclosed pre-pupal males or females) occurredfrom August to December, with a peak in November. Mobile females (adult females emerging from thewhite cysts) were found from August to December, with a peak in August. Parthenogenetic females thatremain in the ruptured white cysts for egg laying were present from August to April, with a peak inNovember. Mobile nymphs (first instar) were also found from August to April, with a peak in December.Yellow cysts were most abundant at depths of 0 to 25 cm. The horizontal survey showed that cysts occurredmostly on the trunk below the ground (trunk of the rootstock), and that almost all occurred in an area of20 cm width around the trunk. These results provide important information for better monitoring of thispest and to develop better methods for and timing of chemical control