Observation of the onset of strong scattering on high frequency acoustic phonons in densified silica glass

The linewidth of longitudinal acoustic waves in densified silica glass is obtained by inelastic x-ray scattering. It increases with a high power alpha of the frequency up to a crossover where the waves experience strong scattering. We find that \alpha is at least 4, and probably larger. Resonance and hybridization of acoustic waves with the boson-peak modes seems to be a more likely explanation for these findings than Rayleigh scattering from disorder.Comment: 4 pages, 4 figures, to appear in Phys. Rev. Letter

Universal behavior of internal friction in glasses below T : anharmonicity vs relaxation

Comparison of the internal friction at hypersonic frequencies between a few K and the glass transition temperature Tg for various glasses brings out general features. At low temperature, internal friction is only weakly dependent on the material. At high temperature but still below Tg the internal friction for strong glasses shows a T-independent plateau in a very wide domain of temperature; in contrast, for fragile glass, a nearly linear variation of internal friction with T is observed. Anharmonicity appears dominant over thermally activated relaxational processes at high temperature.Comment: accepted in Physical Review

Scaling the Temperature-dependent Boson Peak of Vitreous Silica with the high-frequency Bulk Modulus derived from Brillouin Scattering Data

The position and strength of the boson peak in silica glass vary considerably with temperature $T$. Such variations cannot be explained solely with changes in the Debye energy. New Brillouin scattering measurements are presented which allow determining the $T$-dependence of unrelaxed acoustic velocities. Using a velocity based on the bulk modulus, scaling exponents are found which agree with the soft-potential model. The unrelaxed bulk modulus thus appears to be a good measure for the structural evolution of silica with $T$ and to set the energy scale for the soft potentials.Comment: Accepted for publication in Physical Review Letter

The Boson Peak and its Relation with Acoustic Attenuation in Glasses

Experimental results on the density of states and on the acoustic modes of glasses in the THz region are compared to the predictions of two categories of models. A recent one, solely based on an elastic instability, does not account for most observations. Good agreement without adjustable parameters is obtained with models including the existence of non-acoustic vibrational modes at THz frequency, providing in many cases a comprehensive picture for a range of glass anomalies.Comment: 4 pages, 3 figures, Physical Review Letters in pres

Charge migration engineered by localisation: electron-nuclear dynamics in polyenes and glycine

We demonstrate that charge migration can be ‘engineered’ in arbitrary molecular systems if a single localised orbital – that diabatically follows nuclear displacements – is ionised. Specifically, we describe the use of natural bonding orbitals in Complete Active Space Configuration Interaction (CASCI) calculations to form cationic states with localised charge, providing consistently well-defined initial conditions across a zero point energy vibrational ensemble of molecular geometries. In Ehrenfest dynamics simulations following localised ionisation of -electrons in model polyenes (hexatriene and decapentaene) and -electrons in glycine, oscillatory charge migration can be observed for several femtoseconds before dephasing. Including nuclear motion leads to slower dephasing compared to fixed-geometry electron-only dynamics results. For future work, we discuss the possibility of designing laser pulses that would lead to charge migration that is experimentally observable, based on the proposed diabatic orbital approach

Small Angle Scattering by Fractal Aggregates: A Numerical Investigation of the Crossover Between the Fractal Regime and the Porod Regime

Fractal aggregates are built on a computer using off-lattice cluster-cluster aggregation models. The aggregates are made of spherical particles of different sizes distributed according to a Gaussian-like distribution characterised by a mean $a_0$ and a standard deviation $\sigma$. The wave vector dependent scattered intensity $I(q)$ is computed in order to study the influence of the particle polydispersity on the crossover between the fractal regime and the Porod regime. It is shown that, given $a_0$, the location $q_c$ of the crossover decreases as $\sigma$ increases. The dependence of $q_c$ on $\sigma$ can be understood from the evolution of the shape of the center-to-center interparticle-distance distribution function.Comment: RevTex, 4 pages + 6 postscript figures, compressed using "uufiles", published in Phys. Rev. B 50, 1305 (1994

Anharmonic vs. relaxational sound damping in glasses: II. Vitreous silica

The temperature dependence of the frequency dispersion in the sound velocity and damping of vitreous silica is reanalyzed. Thermally activated relaxation accounts for the sound attenuation observed above 10 K at sonic and ultrasonic frequencies. Its extrapolation to the hypersonic regime reveals that the anharmonic coupling to the thermal bath becomes important in Brillouin-scattering measurements. At 35 GHz and room temperature, the damping due to this anharmonicity is found to be nearly twice that produced by thermally activated relaxation. The analysis also reveals a sizeable velocity increase with temperature which is not related with sound dispersion. This suggests that silica experiences a gradual structural change that already starts well below room temperature.Comment: 13 pages with 8 figure

Fluctuating Bond Aggregation: a Model for Chemical Gel Formation

The Diffusion-Limited Cluster-Cluster Aggregation (DLCA) model is modified by including cluster deformations using the {\it bond fluctuation} algorithm. From 3$d$ computer simulations, it is shown that, below a given threshold value $c_g$ of the volumic fraction $c$, the realization of all intra-aggregate bonding possibilities prevents the formation of a gelling network. For $c>c_g$, the sol-gel transition occurs at a time $t_g$ which, in contrast to DLCA, doesnot diverge with the box size. Several results are reported including small angle scattering curves and possible applications are discussed.Comment: RevTex, 9 pages + 3 postscript figures appended using "uufiles". To appear in Phys. Rev. Let

A sulfur-rich pi-electron acceptor derived from 5,5 '-bithiazolidinylidene: charge-transfer complex vs. charge-transfer salt

International audienceNovel pi-electron acceptors are still highly desirable for the formation of conducting salts or as n-dopable semiconductors. We describe here two synthetic approaches to substitute a dicyanovinylidene group, C=C(CN)(2) to a thioketone (C=S) in the recently described DEBTTT acceptor where DEBTTT stands for (E)-3,3'-diethyl-5,5'-bithiazolidinylidene-2,4,2',4'-tetrathione. These electron withdrawing groups enhance the electron accepting ability as demonstrated through electrochemical investigations, without hindering the formation of short intra-and intermolecular S center dot center dot center dot S contacts in the solid state. Association of this acceptor 1 with tetramethyltetrathiafulvalene (TMTTF) and decamethylferrocene (Fe(Cp*)(2)) afforded 1 : 1 adducts which were analyzed by single crystal X-ray diffraction. Combined with vibrational and magnetic properties, it appears that [TMTTF][1] behaves as a neutral charge-transfer complex while [Fe(Cp*)(2)][1] is an ionic salt. The concentration of the spin density on the exocyclic sulfur atoms in 1(-center dot) favors the setting of direct anti-ferromagnetic interactions in [Fe(Cp*)(2)][1

Universal Behaviour of the Superfluid Fraction and Tc of He-3 in 99.5% Open Aerogel

We have investigated the superfluid transition of He-3 in a 99.5% porosity silica aerogel. This very dilute sample shows behaviour intermediary between bulk He-3 and He-3 confined to the denser aerogels previously studied. We present data on both the superfluid transition temperature and the superfluid density and compare our results with previous measurements. Finally, we show that the suppression of the superfluid transition temperature and suppression of the superfluid density of He-3 in aerogel follow a universal relation for a range of aerogel samples.Comment: 4 pages, 5 figures; 1 new figure, minor change