We measured the density of vibrational states (DOS) and the specific heat of various glassy and crystalline polymorphs of ${\mathrm{SiO}}_2$. The typical (ambient) glass shows a well-known excess of specific heat relative to the typical crystal ($\alpha$-quartz). This, however, holds when comparing a lower-density glass to a higher-density crystal. For glassy and crystalline polymorphs with matched densities, the DOS of the glass appears as the smoothed counterpart of the DOS of the corresponding crystal; it reveals the same number of the excess states relative to the Debye model, the same number of all states in the low-energy region, and it provides the same specific heat. This shows that glasses have higher specific heat than crystals not due to disorder, but because the typical glass has lower density than the typical crystal.

Still very little is known on the relaxation dynamics of glasses at the microscopic level due to the lack of experiments and theories. It is commonly believed that glasses are in a dynamical arrested state, with relaxation times too large to be observed on human time scales. Here we provide the experimental evidence that glasses display fast atomic rearrangements within a few minutes, even in the deep glassy state. Following the evolution of the structural relaxation in a sodium silicate glass, we find that this fast dynamics is accompanied by the absence of any detectable aging, suggesting a decoupling of the relaxation time and the viscosity in the glass. The relaxation time is strongly affected by the network structure with a marked increase at the mesoscopic scale associated with the ion-conducting pathways. Our results modify the conception of the glassy state and asks for a new microscopic theory.

The vibrational dynamics of a permanently densified silica glass is compared to the one of an $\alpha$-quartz polycrystal, the silica polymorph of the same density and local structure. The combined use of inelastic x-ray scattering experiments and ab initio numerical calculations provides compelling evidence of a transition, in the glass, from the isotropic elastic response at long wavelengths to a microscopic regime as the wavelength decreases below a characteristic length $\xi$ of a few nanometers, corresponding to about 20 interatomic distances. In the microscopic regime the glass vibrations closely resemble those of the polycrystal, with excitations related to the acoustic and optic modes of the crystal. A coherent description of the experimental results is obtained assuming that the elastic modulus of the glass presents spatial heterogeneities of an average size $a\sim \xi /2\pi$.

Detailed crystallographic information provided by X-ray diffraction (XRD) is complementary to molecular information provided by Raman spectroscopy. Accordingly, the combined use of these techniques allows the identification of an unknown compound without ambiguity. However, a full combination of Raman and XRD results requires an appropriate and reliable reference database with complete information. This is already available for XRD. The main objective of this paper is to introduce and describe the recently developed Raman Open Database (ROD, http://solsa.crystallography.net/rod). It comprises a collection of high-quality uncorrected Raman spectra. The novelty of this database is its interconnectedness with other open databases like the Crystallography Open Database (http://www.crystallography.net/cod and Theoretical Crystallography Open Database (http://www.crystallography.net/tcod/). The syntax adopted to format entries in the ROD is based on the worldwide recognized and used CIF format, which offers a simple way for data exchange, writing and description. ROD also uses JCAMP-DX files as an alternative format for submitted spectra. JCAMP-DX files are compatible to varying degrees with most commercial Raman software and can be read and edited using standard text editors.

Raman, Brillouin light, and x-ray scattering measurements have been carried out to characterize the low-frequency vibrational dynamics of the ${\text{SiO}}_2$ glass as function of its density. The obtained results demonstrate that while the distribution of the low-frequency states in the boson peak range is conserved under densification, these modes do not shift as a function of density as the acoustic modes do. The clear difference between the behavior of the vibrational states in the Boson peak range and that of the acoustic modes, could be explained considering the contribution of specific nonacoustic modes (tetrahedra rotation).

Positron annihilation lifetime spectroscopy is employed to measure the size of the interstitial void spaces characterizing the structure of a set of permanently densified ${\mathrm{SiO}}_{2}$ glasses. The average volume of the voids is markedly affected by the densification process and linearly shrinks by almost an order of magnitude after a relative density variation of 22%. In addition, x-ray diffraction shows that this change of density does not modify appreciably the short range order, which remains organized in ${\mathrm{SiO}}_{4}$ tetrahedra. These results strongly suggest a porous medium description for $v\text{$-${}}{\mathrm{SiO}}_{2}$ glasses where the compressibility and the medium range order are dominated by the density variation of the voids volume up to densities close to that of $$\alpha${}$-quartz.