The broken symmetry in the atomic-scale ordering of glassy versus crystalline solids leads to a daunting challenge to provide suitable metrics for describing the order within disorder, especially on length scales beyond the nearest neighbor that are characterized by rich structural complexity. Here, we address this challenge for silica, a canonical network-forming glass, by using hot versus cold compression to (i) systematically increase the structural ordering after densification and (ii) prepare two glasses with the same high-density but contrasting structures. The structure was measured by high-energy X-ray and neutron diffraction, and atomistic models were generated that reproduce the experimental results. The vibrational and thermodynamic properties of the glasses were probed by using inelastic neutron scattering and calorimetry, respectively. Traditional measures of amorphous structures show relatively subtle changes upon compacting the glass. The method of persistent homology identifies, however, distinct features in the network topology that change as the initially open structure of the glass is collapsed. The results for the same high-density glasses show that the nature of structural disorder does impact the heat capacity and boson peak in the low-frequency dynamical spectra. Densification is discussed in terms of the loss of locally favored tetrahedral structures comprising oxygen-decorated SiSi4 tetrahedra.
We performed terahertz time-domain spectroscopy, low-frequency Raman scattering, and Brillouin light scattering on vitreous glucose to investigate the boson peak (BP) dynamics. In the spectra of is the absorption coefficient], the BP is clearly observed around 1.1 THz. Correspondingly, the complex dielectric constant spectra show a universal resonancelike behavior only below the BP frequency. As an analytical scheme, we propose the relative light-vibration coupling coefficient (RCC), which is obtainable from the combination of the far-infrared and Raman spectra. The RCC reveals that the infrared light-vibration coupling coefficient of the vitreous glucose behaves linearly on frequency which deviates from Taraskin's model of [S. N. Taraskin et al., Phys. Rev. Lett. 97, 055504 (2006)]. The linearity of might require modification of the second term of the model. The measured transverse sound velocity shows an apparent discontinuity with the flattened mode observed in the inelastic neutron scattering study [N. Violini et al., Phys. Rev. B 85, 134204 (2012)] and suggests a coupling between the transverse acoustic and flattened modes.
The anisotropic electronic structure responsible for the antiferromagnetic transition in CeRu2Al10 at the unusually high temperature of T0=28 K was studied using optical conductivity spectra, Ce 3d x-ray photoemission spectra, and band calculation. It was found that the electronic structure in the ac plane is that of a Kondo semiconductor, whereas that along the b axis has a nesting below 32 K (slightly higher than T0). These characteristics are the same as those of CeOs2Al10 [S. Kimura et al., Phys. Rev. Lett. 106, 056404 (2011)]. The c-f hybridization intensities between the conduction and 4f electrons of CeRu2Al10 and CeOs2Al10 are weaker than that of CeFe2Al10, showing no magnetic ordering. These results suggest that the electronic structure with one-dimensional weak c-f hybridization along the b axis combined with two-dimensional strong hybridization in the ac plane causes charge-density wave (CDW) instability, and the CDW state then induces magnetic ordering.
1 November 2015 in Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy
The excess low-frequency vibrational spectrum, called boson peak, and non-affine elastic response are the most important particularities of glasses. Herein, the vibrational and mechanical properties of polymeric glasses are examined by using coarse-grained molecular dynamics simulations, with particular attention to the effects of the bending rigidity of the polymer chains. As the rigidity increases, the system undergoes a glass transition at a higher temperature (under a constant pressure), which decreases the density of the glass phase. The elastic moduli, which are controlled by the decrease of the density and the increase of the rigidity, show a non-monotonic dependence on the rigidity of the polymer chain that arises from the non-affine component. Moreover, a clear boson peak is observed in the vibrational density of states, which depends on the macroscopic shear modulusG. In particular, the boson peak frequency ωBPis proportional to $$\sqrt{G}$$ . These results provide a positive correlation between the boson peak, shear elasticity, and the glass transition temperature.