Rosina C. Ponterio

Communication: An extended model of liquid bridging

Recent phenomenological studies have drawn attention to an appealing effect, observed for the first time in 1893, today known as water-bridge. The phenomenon has been ascribed to unknown properties of water. We report some experimental results showing that, contrary to a widely common belief, the phenomenon is not to be related with water neither with a property of hydrogen bonded networks. Using a very simple model, we show that the liquid bridge phenomenon is originated by electrostatic effects and can be reproduced in any dense fluid with no respect of its peculiar molecular properties. This basic approach is able to reproduce many of the experimentally observed features of the bridge formation. In perspective of future investigations, the possible phenomena responsible of the bridge stability, after its formation, are briefly discussed.

Excess compressibility in binary liquid mixtures

Brillouin scattering experiments have been carried out on some mixtures of molecular liquids. From the measurement of the hypersonic velocities we have evaluated the adiabatic compressibility as a function of the volume fraction. We show how the quadratic form of the excess compressibility dependence on the solute volume fraction can be derived by simple statistical effects and does not imply any interaction among the components of the system other than excluded volume effects. This idea is supported by the comparison of the experimental results with a well-established prototype model, consisting of a binary mixture of hard spheres with a nonadditive interaction potential. This naive model turns out to be able to produce a very wide spectrum of structural and thermodynamic features depending on values of its parameters. An attempt has made to understand what kind of structural information can be gained through the analysis of the volume fraction dependence of the compressibility.

Laser Controlled Synthesis of Noble Metal Nanoparticle Arrays for Low Concentration Molecule Recognition

Nanostructured gold and silver thin films were grown by pulsed laser deposition.Performing the process in an ambient gas (Ar) leads to the nucleation and growth ofnanoparticles in the ablation plasma and their self-organization on the substrate. Thedependence of surface nanostructuring of the films on the deposition parameters is discussedconsidering in particular the number of laser pulses and the ambient gas nature and pressure.The performance of the deposited thin films as substrates for surface-enhanced Ramanspectroscopy (SERS) was tested against the detection of molecules at a low concentration.Taking Raman maps on micrometer-sized areas, the spatial homogeneity of the substrateswith respect to the SERS signal was tested.

A ground level interpretation of the dielectric behavior of diluted alcohol-in-carbon tetrachloride mixtures

The dielectric behavior at room temperature of alcohol/carbon tetrachloride binary mixtures over the whole composition range is analyzed in the low frequency domain (100 kHz). Methanol, ethanol, 1-, 2-propanol, and 1-pentanol are considered. The results are compared with the ideal case as described in the framework of Onsager theory [J. Am. Chem. Soc. 58, 1486 (1936)]. We find that the observed negative deviation from the ideal dielectric constant at high alcohol dilution is almost independent of the alcohol species. This behavior is interpreted as an effect of the presence of closed chainlike alcohol clusters. Good quantitative agreement is found with a simple lattice model describing the equilibrium distribution of alcohol clusters in the framework of the semigrand canonical ensemble. The observed dielectric behavior is then compared with the results of the calorimetric investigations carried out by Otterstedt and Missen [Trans. Faraday Soc. 57, 879 (1962)]. It is concluded that the dielectric and the calorimetric behaviors of these mixtures at high dilutions can be both interpreted consistently as effects of homogeneous association of the alcohol.

Supercooled water escaping from metastability.

The return of supercooled water to a stable equilibrium condition is an irreversible process which, in large enough samples, takes place adiabatically. We investigated this phenomenon in water by fast imaging techniques. As water freezes, large energy and density fluctuations promote the spatial coexistence of solid and liquid phases at different temperatures. Upon synchronously monitoring the time evolution of the local temperature, we observed a sharp dynamic transition between a fast and a slow decay regime at about 266.6 K. We construe the observed phenomenon in terms of the temperature dependence of heat transfers from solid and liquid volumes already at their bulk coexistence temperature towards adjacent still supercooled liquid regions. These findings can be justified by observing that convective motions induced by thermal gradients in a supercooled liquid near coexistence are rapidly suppressed as the nucleated solid fraction overcomes, at low enough temperatures, a characteristic percolation threshold.

Volume crossover in deeply supercooled water adiabatically freezing under isobaric conditions

The irreversible return of a supercooled liquid to stable thermodynamic equilibrium often begins as a fast process which adiabatically drives the system to solid-liquid coexistence. Only at a later stage will solidification proceed with the expected exchange of thermal energy with the external bath. In this paper we discuss some aspects of the adiabatic freezing of metastable water at constant pressure. In particular, we investigated the thermal behavior of the isobaric gap between the molar volume of supercooled water and that of the warmer ice-water mixture which eventually forms at equilibrium. The available experimental data at ambient pressure, extrapolated into the metastable region within the scheme provided by the reference IAPWS-95 formulation, show that water ordinarily expands upon (partially) freezing under isenthalpic conditions. However, the same scheme also suggests that, for increasing undercoolings, the volume gap is gradually reduced and eventually vanishes at a temperature close to the currently estimated homogeneous ice nucleation temperature. This behavior is contrasted with that of substances which do not display a volumetric anomaly. The effect of increasing pressures on the alleged volume crossover from an expanded to a contracted ice-water mixture is also discussed.

Is electrospray emission really due to columbic forces

Electrospray ionization (ESI) is a widely adopted soft ionization method for mass spectroscopy (MS). In spite of the undeniable success of the technique, its mechanisms are difficult to be analytically modelled because the process is characterized by non-equilibrium conditions. The common belief is that the formation of gas-phase ions takes place at the apex of the Taylor cone via electrophoretic charging. The charge balance implies that a conversion of electrons to ions should occur at the metal-liquid interface of the injector needle. We have detected that the above description is based on unproved assumptions which are not consistent with the correct evaluation of the problem. The comparison between experiments performed under the usual geometry and observations obtained under symmetric field configurations suggests that the emitted droplets cannot be significantly charged or, at least, that any possible ionization mechanism is so poorly efficient to ensure that columbic forces cannot play a major role in jet formation, even in cases where the liquid consists of a solution of ionic species. Further work is required to clearly understand how ionization occurs in ESI-MS.

SERS and DFT study of indigo adsorbed on silver nanostructured surface

Surface-enhanced Raman spectroscopy has emerged as a widely used tool in the identification of organic dyes in works of art. Indigo is among the most used organic pigment, its identification can therefore give important information about the provenience and the making of the investigated work of art. In this work, we combine Surface Enhanced Raman Spectroscopy (SERS) experiments with density functional theory (DFT) computations of the Raman frequencies of indigo and an indigo molecule adsorbed onto a silver surface made of 16 silver atoms. The SERS spectrum of a molecule adsorbed on a metallic surface, in fact, can differ from the corresponding Raman one. The knowledge and the comprehension of the SERS spectrum then are mandatory in dyes identification. Experimental SERS spectra were acquired using ad hoc SERS active substrates consisting of pulsed laser ablated silver nanoparticles deposited onto a polishing sheet. The polishing sheet surface roughness is able to remove some pigments grains from the surface of a work of art without damage. DFT calculations provide a good description of the observed SERS spectra, in particular, the indigo-Ag16 structure gives a better description with respect to structures where only one or two silver atoms attached to the indigo molecule are considered.

A spectroscopic approach to the study of organic pigments in the field of cultural heritage

Characterization of pigments in archaeological finds requires an experimental approach able to avoid the destruction or perturbation of the artwork. Surface Enhanced Raman Spectroscopy technique may provide useful information in terms of chemical composition by using very small sample quantities and without samples manipulation. In this paper some pigments and an archeological find, discovered in Messina, have been analyzed with new SERS substrates prepared with Pulsed Laser Deposition (PLD) technique with two different instrumentations. In both cases we quenched the fluorescence phenomena and enhanced Raman peaks.

Electrically induced birefringence in nanoparticle dispersions for electrorheological applications

Recently, the observation of an anomalously large electrorheological effect in the dispersion of nanosized particles of titania in octanoid acid has been reported. Such an enhanced effect was not observed in the similar dispersion of micrometric particles or in more conventional suspensions of silica in silicon oil. It was suggested that this effect could be promoted by the formation of a thin layer of solvent molecules on the surface of the titania particles. We propose the measurement of electrically induced optical birefringence as a suitable independent method for testing this working hypothesis.In this paper, we report the results from the investigations of the dilute dispersions of 32?nm TiO2 particles in two insulating fluids: silicone oil and octanoic acid. A comparison of the experimental birefringence data with the theoretical predictions suggests that TiO2 nanoparticles behave like permanent electric dipoles, although induced dipoles are expected in the case of the titania material. The source of such behaviour has been individuated at the particle/solvent interface and the different possibilities of the permanent dipole origin are discussed. The lower value of the dipole moment observed in octanoic acid dispersion is explained in terms of a specific particle/solvent interaction leading to the formation of a solvent coating around the particle. The results highlight that electro-optical properties are related to electrorheological performance and that both methods can be considered as supportive for testing electrically driven phenomena in complex fluids.