Inelastic neutron scattering study of water in hydrated LTA-type zeolites

The vibrational dynamics of water molecules encapsulated in synthetic Na-A and Mg-exchanged A zeolites were studied versus temperature by inelastic neutron scattering (INS) measurements (30-1200 cm(-1)) as a function of the induced ion-exchange percentage by using the indirect geometry tof spectrometer TOSCA at the ISIS pulse neutron facility (RAL, UK). The experimental INS spectra were compared with those of ice Ih to characterize the structural changes induced by confinement on the H2O hydrogen-bonded network. We observed, after increasing the Mg2+ content, a tendency of water molecules to restore the bulklike arrangements together with more hindered dynamics. These results are confirmed by the analysis of the evaluated one-phonon amplitude-weighted proton vibrational density of states aimed, in particular, to follow the evolution of the water molecules librational mode region.     

Characterization of blue decorated Renaissance pottery fragments from Caltagirone (Sicily,Italy)

Renaissance blue decorated pottery fragments from the archaeological site of Caltagirone (Sicily, Italy) were analysed by scanning electron microscopy – energy dispersive X-ray spectrometry (SEM/EDS). The samples were dated back to 16th century AD on the basis of archaeological observations. The micro-chemical analyses were performed on the ceramic body and the surface decorated layer of the samples. Particularly, the investigation was addressed the characterization of the coating blue decorations. The obtained results allowed us to clearly identify smalt as pigment. Also the presence of arsenic (As) was revealed and the Co/As ratio values were calculated and related to the different process used for the pigment preparation. Further spectroscopic analyses, performed through X-ray absorbance spectroscopy (XAS), carried out at the Co K-edge, confirmed the micro-analytical results and permitted us to identify the oxidation form and the local environment of cobalt atoms. PACS  81.05.Mh; 82.80.-d; 68.37.Hk     

Intramolecular electron transfer in heterosubstituted benzene derivatives as probed by dissociative electron attachment

The electron transmission and dissociative electron attachment spectra of the 1-chloroalkyl benzene derivatives, C(6)H(5)(CH(2))(3)Cl and C(6)H(5)(CH(2))(4)Cl, and of the sulfur and silicon derivatives, C(6)H(5)SCH(2)Cl, C(6)H(5)Si(CH(3))(2)CH(2)Cl and C(6)H(5)CH(2)Si(CH(3))(2)CH(2)Cl, are presented for the first time. The relative Cl(-) fragment anion currents generated by electron attachment to the benzene pi* LUMO are measured in the series C(6)H(5)(CH(2))(n)Cl, with n = 1-4, and in the heteroatomic compounds. The Cl(-) yield reflects the rate of intramolecular electron transfer between the pi-system and the remote chlorine atom, which in turn depends on the extent of through-bond coupling between the localized pi* and sigma*(Cl-C) orbitals. In compounds C(6)H(5)(CH(2))(n)Cl the Cl(-) current rapidly decreases with increasing length of the saturated chain. This decrease is significantly attenuated when a carbon atom of the alkyl skeleton is replaced with a third-row heteroatom. This greater ability to promote through-bond coupling between the pi* and sigma*(Cl-C) orbitals is attributed to the sizably lower energy of the empty sigma*(S-C) and sigma*(Si-C) orbitals with respect to the sigma*(C-C) orbitals. In the sulfur derivative the increase of the Cl(-) current is larger than in the silicon analogue. In this case, however, other negative fragments are observed, due to dissociation of the S-C bonds.     

Raman spectroscopy: Probing dynamics of water molecules confined in nanoporous silica glasses

In order to explore the influence of nanoscopic confinement on the vibrational properties of H-bonded liquids, we performed a detailed Raman scattering study, as a function of temperature, on water confined in 75 ? and 200 ? pores of a Gelsil glass. A detailed evaluation of the observed changes in the O-H stretching profile has been achieved by decomposing the O-H band into individual components, corresponding to those found for bulk water and associated to different levels of water connectivity. As main result, a similar effect produced by enlarging pore diameter and lowering T has been put into evidence. Again, the “structure-breaker” role of the GelSil glass on physisorbed water is confirmed and shown to be enhanced by the diminishing of the pore size.     

A FT-IR absorption analysis of vibrational properties of water encaged in NaA zeolites: evidence of a "structure maker" role of zeolitic surface

We performed, in the O-H stretching region, Fourier-transform Infrared (FT-IR) Absorption measurements for investigating the vibrational dynamics on water confined in NaA zeolite, vs. temperature and for different hydration percentages. The spectral substructure of the O-H stretching band is explained postulating the existence of three major components centred at approximately 3290 cm(-1) (omega(1)), approximately 3470 cm(-1) (omega(2)), approximately 3590 cm(-1) (omega(3)), with different dynamical properties traced over the full T-range investigated.     

Probing pentacene polymorphs by lattice dynamics calculations

We have performed a lattice dynamics calculation to compute the "inherent structures" of minimum potential energy for pentacene, starting from available X-ray data. The calculation shows that two distinct bulk crystalline phases of pentacene exist, with very subtle structural differences but clearly different phonon spectra. The method of crystal growth (from solution or vapor) is not the determining factor for obtaining either structure.     

Effect of substrate temperature on electrical and magnetic properties of epitaxial La1−x Pb x MnO3 films

Epitaxial La_1−x Pb _x MnO₃ (LPMO) thin films, grown on (100) SrTiO₃ substrates by laser ablation technique at different temperatures between 600 and 850°C, have been characterized for electrical and magnetic properties. The temperature dependence of resistivity showed that the metal-insulator transition temperature (T _MI) decreases with increasing substrate temperature, which has been attributed to decrease in Pb content in the filsm. The YBa₂Cu₃O _x /La_1−x MnO₃ heterostructures, exhibiting both superconductivity and ferromagnetism, have been fabricated.     

Role of the solvent in the dynamical transitions of proteins: the case of the lysozyme-water system

We study the dynamics of hydration water in the protein lysozyme in the temperature range 180 K相似文献