The structure-thermodynamic stability relationship in vitreous silica is investigated using machine learning and a library of 24,157 inherent structures generated from melt-quenching and replica exchange molecular dynamics simulations. We find the thermodynamic stability, i.e., enthalpy of the inherent structure ($e_{\mathrm{IS}}$), can be accurately predicted by both linear and nonlinear machine learning models from numeric structural descriptors commonly used to characterize disordered structures. We find short-range features become less indicative of thermodynamic stability below the fragile-to-strong transition. On the other hand, medium-range features, especially those between 2.8-~6 $\unicode{x212B}$;, show consistent correlations with $e_{\mathrm{IS}}$ across the liquid and glass regions, and are found to be the most critical to stability prediction among features from different length scales. Based on the machine learning models, a set of five structural features that are the most predictive of the silica glass stability is identified.
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 incre…
The attenuation of longitudinal acoustic phonons up to frequencies nearing 250 GHz is measured in vitreous silica with a picosecond optical technique. Taking advantage of interferences on the probe beam, difficulties encountered in early pioneering experiments are alleviated. Sound damping at 250 GHz and room temperature is consistent with relaxation dominated by anharmonic interactions with the thermal bath, extending optical Brillouin scattering data. Our result is at variance with claims of a recent deep-UV experiment which reported a rapid damping increase beyond 100 GHz. A comprehensive p…
A previous inelastic UV scattering experiment on silica glass is reproduced using a high grade superpolished sample. In the pristine sample condition, surface scattering is not observable compared to Rayleigh scattering from the bulk. However, exposure to a fluence of the order of 100 J/cm$^2$ at photon energies slightly below the electronic gap generates observable surface damage. This occurs after a few hours illumination with the monochromatic spectrometer beam. No anomaly in the Brillouin linewidth was found up to an excitation energy of 7.8 eV.
Sound velocities of vitreous silica are measured under He compression in the pressure range 0-6 GPa by Brillouin light scattering. It is found that the well-known anomalous maximum in the pressure dependence of the compressibility is suppressed by He incorporation into the silica network. This shows that the elastic anomaly relates to the collapse of the largest interstitial voids in the structure. The huge difference between the static and the acoustic compressibilities indicates that the amount of incorporated helium still increases at 6 GPa.
We report a molecular dynamics simulation study of the sound waves in vitreous silica in the mesoscopic exchanged momentum range. The calculated dynamical structure factors are in quantitative agreement with recent experimental inelastic neutron and x-ray scattering data. The analysis of the longitudinal and transverse current spectra allows to discriminate between opposite interpretations of the existing experimental data in favour of the propagating nature of the high frequency sound waves.
We perform classical molecular-dynamics simulation to study the effect of densification on the vibrational spectrum of a model silica glass. We concentrate this study on the so-called Boson peak and compare our results, obtained from a direct diagonalization of the dynamical matrix, with experimental Raman data. We show that, upon densification, the position of the Boson peak shifts towards higher frequencies while its magnitude decreases which is in agreement with a recent experimental study.
We computer model a free-standing vitreous silica bilayer which has recently been synthesized and characterized experimentally in landmark work. Here we model the bilayer using a computer assembly procedure that starts from a single layer of amorphous graphene, generated using a bond switching algorithm from an initially crystalline graphene structure. Next each bond is decorated with an oxygen atom and the carbon atoms are relabeled as silicon. This monolayer can be now thought of as a two dimensional network of corner sharing triangles. Next each triangle is made into a tetrahedron, by raisi…
The dynamical structure factor (S(Q,E)) of vitreous silica has been measured by Inelastic X-ray Scattering varying the exchanged wavevector (Q) at fixed exchanged energy (E) - an experimental procedure that, contrary to the usual one at constant Q, provides spectra with much better identified inelastic features. This allows the first direct evidence of Brillouin peaks in the S(Q,E) of SiO_2 at energies above the Boson Peak (BP) energy, a finding that excludes the possibility that the BP marks the transition from propagating to localised dynamics in glasses.
New temperature dependent inelastic x-ray (IXS) and Raman (RS) scattering data are compared to each other and with existing inelastic neutron scattering data in vitreous silica (v-SiO_2), in the 300 - 1775 K region. The IXS data show collective propagating excitations up to Q=3.5 nm^-1. The temperature behaviour of the excitations at Q=1.6 nm^-1 matches that of the boson peak found in INS and RS. This supports the acoustic origin of the excess of vibrational states giving rise to the boson peak in this glass.
We present a numerical simulation study of the density-dependence (rho = 2.2 - 4.0 g/cm^3) of the high-energy collective dynamics in vitreous silica at mesoscopic wavevectors (Q = 1 - 18 nm^-1). The density-dependence of the longitudinal and transverse current spectra provides evidence that the excess modes observed in the density of states of this and many other glasses, i.e. the Boson Peak, arises from the high-Q limit of the quasi-transverse acoustic branch. This conclusion emerges from the comparison of the numerical results with the experimentally observed energy-shift and intensity varia…
We use extensive classical molecular dynamics simulations to calculate the thermal conductivity of a model silica glass. Apart from the potential parameters, this is done with no other adjustable quantity and the standard equations of heat transport are used directly in the simulation box. The calculations have been done between 10 and 1000 Kelvin and the results are in good agreement with the experimental data at temperatures above 20K. The plateau observed around 10K can be accounted for by correcting our results taking into account finite size effects in a phenomenological way.
The incoherent approximation for the determination of the vibrational density of states of glasses from inelastic neutron or x-ray scattering data is extended to treat the coherent scattering. The method is applied to new room temperature measurements of vitreous silica and germania on the thermal time-of-flight spectrometer IN4 at the High Flux Reactor in Grenoble. The inelastic dynamic structure factor at the boson peak turns out to be reasonably well described in terms of a mixture of rotation and translation of practically undistorted SiO4 or GeO4 tetrahedra. The translational component ex…
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.
The temperature dependence of the x-ray scattering in the region below the first sharp diffraction peak was measured for silica glasses with low and high OH content (GE-124 and Corning 7980). Data were obtained upon scanning the temperature at 10, 40 and 80 K/min between 400 K and 1820 K. The measurements resolve, for the first time, the hysteresis between heating and cooling through the glass transition for silica glass, and the data have a better signal to noise ratio than previous light scattering and differential thermal analysis data. For the glass with the higher hydroxyl concentration t…
We compare the vibrational properties of model SiO_2 glasses generated by molecular-dynamics simulations using the effective force field of van Beest et al. (BKS) with those obtained when the BKS structure is relaxed using an ab initio calculation in the framework of the density functional theory. We find that this relaxation significantly improves the agreement of the density of states with the experimental result. For frequencies between 14 and 26 THz the nature of the vibrational modes as determined from the BKS model is very different from the one from the ab initio calculation, showing th…
We report an experimental and numerical study of femtosecond multi-pulse laser-induced densification in vitreous silica (v-SiO2) and its signature in Raman spectra. We compare the experimental findings to recently developed molecular dynamics (MD) approach accounting for bond-breaking due to laser irradiation, together with a dynamical matrix approach and bond polarizability model based on first-principle calculations for the estimation of Raman spectra. We observe two stages of the laser-induced densification and Raman spectrum evolution: growth during several hundreds of pulses followed by f…
We report time-resolved photoluminescence spectra of point defects in amorphous silicon dioxide (silica), in particular the decay kinetics of the emission signals of extrinsic Oxygen Deficient Centres of the second type from singlet and directly-excited triplet states are measured and used as a probe of structural inhomogeneity. Luminescence activity in sapphire ($α$-Al$_2$O$_3$) is studied as well and used as a model system to compare the optical properties of defects in silica with those of defects embedded in a crystalline matrix. Only for defects in silica, we observe a variation of the de…
The dynamics of silica displays an Arrhenius temperature dependence, classifying silica as a strong glass-former. Using recently developed concepts to analyse the potential energy landscape one can get a fundamental understanding of the long-range transport of silica. It can be expressed in terms of properties of the thermodynamics as well as local relaxation processes, thereby extending the phenomenological standard picture of a strong glass-former. The local relaxation processes are characterized by complex correlated sequences of bond breaking and reformation processes.
The thermodynamic properties of subsystems in strong interaction with the neighborhood can largely differ from the standard behavior. Here we study the thermodynamic properties of rings and triplets in equilibrated disordered 2D-silica. Their statistics follows a Boltzmann behavior, albeit with a strongly reduced temperature. This effective temperature strongly depends on the length scale of the chosen subsystem. From a systematic analysis of the 1D Ising model and an analytically solvable model we suggest that these observations reflect the presence of strong local positive energy correlation…
We discuss a novel approach that allows to obtain effective potentials from ab initio trajectories. Our method consists in fitting the weighted radial distribution functions obtained from the ab initio data with the ones obtained from simulations with the effective potential, and using the parameters of the latter as fitting variables. As a case study, we consider the example of amorphous silica, a material that is highly relevant in the field of glass science as well as in geology. Our approach is able to obtain an effective potential that gives a better description with respect to structural…
The dynamic structure factor, S(Q,w), of vitreous silica, has been measured by inelastic X-ray scattering in the exchanged wavevector (Q) region Q=4-16.5 nm-1 and up to energies hw=115 meV in the Stokes side. The unprecedented statistical accuracy in such an extended energy range allows to accurately determine the longitudinal current spectra, and the energies of the vibrational excitations. The simultaneous observation of two excitations in the acoustic region, and the persistence of propagating sound waves up to Q values comparable with the (pseudo-)Brillouin zone edge, allow to observe a po…
In this work, we revisit the fragile-to-strong transition (FTS) in the simulated BKS silica from the perspective of microscopic dynamics in an effort to elucidate the dynamical behaviors of fragile and strong glass-forming liquids. Softness, which is a machine-learned feature from local atomic structures, is used to predict the microscopic activation energetics and long-term dynamics. The FTS is found to originate from a change in the temperature dependence of the microscopic activation energetics. Furthermore, results suggest there are two diffusion channels with different energy barriers in …
The continuous development of synchrotron-based experimental techniques in the X-ray range provides new possibilities to probe the structure and the dynamics of bulk materials down to inter-atomic distances. However, the interaction of intense X-ray beams with matter can also induce changes in the structure and dynamics of materials. A reversible and non-destructive beam induced dynamics has recently been observed in X-ray photon correlation spectroscopy experiments in some oxide glasses at sufficiently low absorbed doses, and is here investigated in a (Li$_2$O)$_{0.5}$(B$_2$O$_3$)$_{0.5}$ gla…
