F. Scarponi

Light Scattering Spectra of Water in Trehalose Aqueous Solutions: Evidence for Two Different Solvent Relaxation Processes

Light scattering spectra on aqueous solutions of trehalose were recorded in a wide frequency range combining the use of a double monochromator and a multipass Fabry-Perot interferometer. Experimental results indicate the presence of a slow relaxation mode related to the solute dynamics, which is clearly separated from the solvent one. The spectral analysis reveals the existence of two separate solvent relaxation processes assigned to hydrating and bulk water molecules. The picosecond dynamics of water molecules directly interacting with the solute (proximal water) is consistently delayed with the corresponding relaxation time increase is about 5-6 times compared to the bulk. The slowing down induced by the sugar on the water dynamics mainly involves a restricted hydration layer constituted of 16-18 water molecules. These results improve our knowledge about the influence of carbohydrates on the fast rearrangement dynamics of water and may serve as a model to gain important insight on basic solvation properties of other biorelevant systems in aqueous media.

Density fluctuations in the intermediate glass-former glycerol: A Brillouin light scattering study

Brillouin scattering has been used to measure the dynamic structure factor of glycerol as a function of temperature from the high temperature liquid to the glassy state. Our investigation aims at understanding the number and the nature of the relaxation processes active in this prototype glass forming system in the high frequency region. The associated character of glycerol is reflected by a rather simple relaxation pattern, while the contributions coming from intramolecular channels are negligible in the GHz frequency region. The temperature behavior of the characteristic frequency and lifetime of the longitudinal acoustic modes is analyzed, suggesting that a phenomenological model which only includes the structural (α) process and the unrelaxed viscosity is able to catch the leading contributions to the dynamics of the density fluctuations. This ansatz is also supported by a combined analysis of light and inelastic x-ray scattering spectra. The temperature dependence of the characteristic time of the α-...

Communication: High-frequency acoustic excitations and boson peak in glasses: A study of their temperature dependence.

The results of a combined experimental study of the high-frequency acoustic dynamics and of the vibrational density of states (VDOS) as a function of temperature in a glass of sorbitol are reported here. The excess in the VDOS at approximately 4.5 meV over the Debye, elastic continuum prediction (boson peak) is found to be clearly related to anomalies observed in the acoustic dispersion curve in the mesoscopic wavenumber range of few nm(-1). The quasiharmonic temperature dependence of the acoustic dispersion curves offers a natural explanation for the observed scaling of the boson peak with the elastic medium properties.

Hydrophobic hydration of tert-butyl alcohol studied by Brillouin light and inelastic ultraviolet scattering

The longitudinal viscosity of diluted water-tert-butyl alcohol solutions in the 10 GHz frequency region has been measured by means of Brillouin light scattering and inelastic ultraviolet scattering. The main advantage of our hypersonic investigation compared to more traditional ultrasonic measurements is that in the gigahertz frequency range slow relaxation processes involving the alcohol dynamics are completely unrelaxed, so that the measured viscosity mainly originates from the hydrogen bond restructuring of water. In contrast with previous determinations, we estimate an activation energy which is independent from the alcohol mole fraction up to X = 0.1, and comparable to that of bulk water. A simple two-component model is used to describe the steep increase of viscosity with increasing alcohol mole fraction, and a retardation factor 1.7 ± 0.2 is found between the relaxation times of hydration and bulk water. These findings endorse a dynamic scenario where the slowing down of hydration water is mainly due to a reduction of configurational entropy and does not involve an arrested, icelike, dynamics.

Influence of Glycerol on the Structure and Thermal Stability of Lysozyme: A Dynamic Light Scattering and Circular Dichroism Study

Photon correlation spectroscopy and circular dichroism have been used to study the role of hydration in the structure and thermostability of the model protein lysozyme in water-glycerol mixtures. Two cases have been considered: water-rich and glycerol-rich regimes of concentrations. We follow the thermal denaturation both by optical spectral changes and hydrodynamic radius variations. This methodology allows us to emphasize the relevant role played by hydrophobic interactions during the process in aqueous solutions and, in glycerol, to distinguish the non-cooperative melting of secondary structure, supporting the view of a protein transition to a molten globule-like state.

Onset of the α-relaxation in the glass-forming solution LiCl–6H2O revealed by Brillouin scattering techniques

We measured the dynamic structure factor of the liquid and glassy phases of the LiCl-6H(2)O solution by means of inelastic scattering of radiation in the visible, UV, and x-ray range, between 1 GHz and 10 THz, and by means of photon-correlation spectroscopy, between 0.01 Hz and 20 kHz. The measurements were performed in the temperature range between 353 and 80 K. Our data show that a single-relaxation process exists at high temperature, which has features similar to those of the single relaxation of pure water. Upon cooling the system below approximately 220 K, this single mode starts to differentiate two processes, a structural (alpha-) and a secondary (beta-) relaxation. As the temperature is decreased, the beta-relaxation is the vanishing continuation of the single, high-temperature process, while the onset of the alpha-relaxation occurs at the expense of the beta-process.

Acoustic excitations in glassy sorbitol and their relation with the fragility and the boson peak.

We report a detailed analysis of the dynamic structure factor of glassy sorbitol by using inelastic X-ray scattering and previously measured light scattering data [B. Ruta, G. Monaco, F. Scarponi, and D. Fioretto, Philos. Mag. 88, 3939 (2008)]. The thus obtained knowledge on the density-density fluctuations at both the mesoscopic and macroscopic length scale has been used to address two debated topics concerning the vibrational properties of glasses. The relation between the acoustic modes and the universal boson peak (BP) appearing in the vibrational density of states of glasses has been investigated, also in relation with some recent theoretical models. Moreover, the connection between the elastic properties of glasses and the slowing down of the structural relaxation process in supercooled liquids has been scrutinized. For what concerns the first issue, it is here shown that the wave vector dependence of the acoustic excitations can be used, in sorbitol, to quantitatively reproduce the shape of the boson peak, supporting the relation between BP and acoustic modes. For what concerns the second issue, a proper study of elasticity over a wide spatial range is shown to be fundamental in order to investigate the relation between elastic properties and the slowing down of the dynamics in the corresponding supercooled liquid phase.

Nonergodicity factor, fragility, and elastic properties of polymeric glassy sulfur.

We present a detailed investigation of the vibrational dynamics of glassy sulfur (g-S). The large frequency range spanned in this study has allowed us to carefully scrutinize the elastic properties of g-S and to analyze their relation to various features of both the glassy and the liquid state. In particular, the acoustic properties of g-S present a quasi-harmonic behavior in the THz frequency range, while at lower frequency, in the GHz range, they are affected by a strong anharmonic contribution. Moreover, the high frequency (THz) dynamics of g-S does not present signatures of the elastic anomalies recently observed in a number of glasses. Despite this apparent contradiction, we show that this finding is not in disagreement with the previous ones. Finally, by considering the correct long wavelength limit of the density fluctuations in the glassy state, we estimate the continuum limit of the nonergodicity factor and we investigate recently proposed relations between the fast dynamics of glasses and the slow dynamics of the corresponding viscous melts.

Brillouin light scattering study of glassy sorbitol

Brillouin light scattering has been used to investigate the density fluctuations of the fragile glass-former sorbitol in the GHz frequency range and at temperatures between 20 and 294 K. Longitudinal acoustic sound velocity and attenuation data are here reported and discussed. These data are used to test the existence of a correlation between elastic properties of glasses and viscous properties of the corresponding deeply undercooled melts above the glass transition temperature, T g . In particular, and as for other fragile systems, the ratio of the vibrational to the relaxational compressibility at T g is found to be basically independent of fragility.

Origin of the λ transition in liquid sulfur

T. Scopigno, S.N. Yannopoulos, F. Scarponi, K.S. Andrikopoulos, D. Fioretto, G. Ruocco Research center SOFT-INFM-CNR, Università di Roma “La Sapienza,” I-00185, Roma, Italy 2 ICE/HT-FORTH GR-26504, Patras, Greece 3 Dipartimento di Fisica, Universitá di Perugia, via Pascoli, I-06123 Perugia, Italy 4 Physics Division, School of Technology, Aristotle University of Thessaloniki, GR-54124, Thessaloniki, Greece and 5 Dipartimento di Fisica, Universitá di Roma ”La Sapienza”, 00185 Roma, Italy (Dated: February 1, 2008)