Glasses have a large excess of low-frequency vibrational modes in comparison with continuous elastic body, the so-called Boson Peak, which appears to correlate with several crucial properties of glasses, such as transport or fragility. I review recent results showing that the Boson Peak is a necessary consequence of the weak connectivity of the solid. I explain why in assemblies repulsive spheres the boson peak shifts up to zero frequency as the pressure is lowered toward the jamming threshold, and derive the corresponding exponent. I show how these ideas capture the main low-frequency features of the vibrational spectrum of amorphous silica. These results extend arguments of Phillips on the presence of floppy modes in under-constrained covalent networks to glasses where the covalent network is rigid, or when interactions are purely radial.
In a recent letter (Phys. Rev. Lett. 84, 4629 (2000)), Lacks presents evidence of a first order amorphous-amorphous transition in silica at T=0. He calculates the free energy along a path of compression and successive decompression of a sample of 108 SiO2 units. The free energy of the two branches cross each other, and this is interpreted as evidence of a first order transition. We show that this conclusion does not follow from the shown data, since qualitatively the same phenomenology is obtained in a model where a first order transition does not exist.
We have studied the photoinduced transformation of small rings (3-membered) in amorphous silica by Car-Parrinello simulations. The process of ring opening leading to the formation of a couple of paramagnetic centers, namely an E' and a non-bridging-oxygen hole center (NBOHC), has been proposed experimentally to occur in silica exposed to F2 laser irradiation (at 7.9 eV). By using a new scheme for the simulation of rare events in ab-initio molecular dynamics (Iannuzzi, Laio and Parrinello, Phys. Rev. Lett. 90, 238303 (2003)), we have identified the transformation path for the opening of a 3-mem…
The effect of silica-promotion on the reduction of iron oxides in hydrogen was investigated using in situ X-ray diffraction and aberration-corrected transmission electron microscopy to understand the mechanism of reduction and the identity of the iron(II) silicate phase that has historically been designated as the cause of the iron-silica interaction in such materials. In the absence of a silica promoter the reduction of hematite to α-Fe proceeds via magnetite. Silica promoted amorphous iron oxide is reduced to α-Fe via stable magnetite and wüstite phases. During reduction of silica-promoted i…
Amorphous silica deforms viscoplastically at elevated temperatures, as is common for brittle glasses. The key mechanism of viscoplastic deformation involves interatomic bond switching, which is known to be a thermally activated process. In this study, through systematic in-situ compression tests by scanning electron microscopy, the viscoplastic deformation of amorphous silica is observed without thermal activation. Furthermore, ductility does not increase monotonically with acceleration voltage and current density of the SEM e-beam but is maximized by a factor of three at a specific accelerati…
A core-softened model of a glass forming fluid is numerically studied in the limit of very low temperatures. The model shows two qualitatively different behaviors depending on the strength of the attraction between particles. For no or low attraction, the changes of density as a function of pressure are smooth, although hysteretic due to mechanical metastabilities. For larger attraction, sudden changes of density upon compressing and decompressing occur. This global mechanical instability is correlated to the existence of a thermodynamic first-order amorphous-amorphous transition. The two diff…
We report experimental evidence of the existence of two variants of the E' gamma centers induced in silica by gamma rays at room temperature. The two variants are distinguishable by the fine features of their line shapes in paramagnetic resonance spectra. These features suggest that the two E' gamma differ for their topology. We find a thermally induced interconversion between the centers with an activation energy of about 34 meV. Hints are also found for the existence of a structural configuration of minimum energy and of a metastable state.
Microstructural dynamics in amorphous particle packings is commonly probed by quantifying particle displacements. While rigidity in particle packings emerges when displacement of particles are hindered, it is not obvious how the typically disordered displacement metrics connect to mechanical response. Particle rotations, in contrast, are much less sensitive to confinement effects, while still sensitive to the mechanics of the packing. So far, little attention has been paid to connect microscopic rotational motion to mechanics of athermal amorphous packings. We demonstrate through experimental …
A combination of classical molecular dynamics (MD) and ab initio Car-Parrinello molecular dynamics (CPMD) simulations is used to investigate the adsorption of water on a free amorphous silica surface. From the classical MD SiO_2 configurations with a free surface are generated which are then used as starting configurations for the CPMD.We study the reaction of a water molecule with a two-membered ring at the temperature T=300K. We show that the result of this reaction is the formation of two silanol groups on the surface. The activation energy of the reaction is estimated and it is shown that …
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…
We investigate the adsorption and diffusion behaviors of CO2, CH4, and N2 in interfacial systems composed of a polymer of intrinsic microporosity (PIM-1) and amorphous silica using grand canonical Monte Carlo (GCMC) and molecular dynamics (MD) simulations. We build model systems of mixed matrix membranes (MMMs) with PIM-1 chains sandwiched between silica surfaces. Gas adsorption analysis using GCMC simulations shows that gas molecules are preferentially adsorbed in microcavities distributed near silica surfaces, resulting in an increase in the solubility coefficients of CO2, CH4, and N2 compar…
Crystalline and amorphous nanoparticles of silicon in thin silica layers were examined by transmission electron microscopy (TEM), electron energy loss spectroscopy (EELS) and x-ray photoelectron spectroscopy (XPS). We used XPS data in the form of the Auger parameter to separate initial and final state contributions to the Si$_{2p}$ energy shift. The electrostatic charging and electron screening issues as well as initial state effects were also addressed. We show that the chemical shift in the nanocrystals is determined by initial state rather than final state effects, and that the electron scr…
Samples of amorphous MgSiO_3 annealed at temperature steps leading up to their crystallisation temperature show a rise in photoluminescence activity, peaking at ~450C. The photoluminescence band has a main peak at 595nm and a weaker peak at 624nm. We present laboratory data to show that the maximum in photoluminescence activity is related to substantial structural reordering that occurs within a relatively narrow temperature range. We attribute the origin of the photoluminescence to non-bridging oxygen hole centre defects, which form around ordered nano-sized domain structures as a result of t…
Liquids and solids are two fundamental states of matter. However, due to the lack of direct experimental determination, our understanding of the 3D atomic structure of liquids and amorphous solids remained speculative. Here we advance atomic electron tomography to determine for the first time the 3D atomic positions in monatomic amorphous materials, including a Ta thin film and two Pd nanoparticles. We observe that pentagonal bipyramids are the most abundant atomic motifs in these amorphous materials. Instead of forming icosahedra, the majority of pentagonal bipyramids arrange into networks th…
Mechanically stable sphere packings are generated in three-dimensional space using the discrete element method, which span a wide range in structural order, ranging from fully amorphous to quasi-ordered structures, as characterized by the bond orientational order parameter. As the packing pressure, $p$, varies from the marginally rigid limit at the jamming transition ($p \approx 0$) to that of more robust systems ($p \gg 0$), the coordination number, $z$, follows a familiar scaling relation with pressure, namely, $Δz = z - z_c \sim p^{1/2}$, where $z_c = 2d = 6$ ($d=3$ is the spatial dimension…
The interface chemistry of silicon nanocrystals (NCs) embedded in amorphous oxide matrix is studied through molecular dynamics simulations with the chemical environment described by the reactive force field model. Our results indicate that the Si NC-oxide interface is more involved than the previously proposed schemes which were based on solely simple bridge or double bonds. We identify different types of three-coordinated oxygen complexes, previously not noted. The abundance and the charge distribution of each oxygen complex is determined as a function of the NC size as well as the transition…
The structural and dynamic properties of silica melts under high pressure are studied using molecular dynamics (MD) computer simulation. The interactions between the ions are modeled by a pairwise-additive potential, the so-called CHIK potential, that has been recently proposed by Carre et al. The experimental equation of state is well-reproduced by the CHIK model. With increasing pressure (density), the structure changes from a tetrahedral network to a network containing a high number of five- and six-fold Si-O coordination. In the partial static structure factors, this change of the structur…
Disordered hyperuniformity (DHU) is a recently proposed new state of matter, which has been observed in a variety of classical and quantum many-body systems. DHU systems are characterized by vanishing infinite-wavelength density fluctuations and are endowed with unique novel physical properties. Here we report the first discovery of disordered hyperuniformity in atomic-scale 2D materials, i.e., amorphous silica composed of a single layer of atoms, based on spectral-density analysis of high-resolution transmission electron microscope images. Subsequent simulations suggest that the observed DHU …
We studied the optical absorption induced by 4.7eV pulsed laser radiation on Ge-doped a-SiO2 synthesized by a sol-gel technique. The absorption spectra in the ultraviolet spectral range were measured during and after the end of irradiation with an in situ technique, evidencing the growth of an absorption signal whose profile is characterized by two main peaks near 4.5eV and 5.7eV and whose shape depends on time. Electron spin resonance measurements performed ex situ a few hours after the end of exposure permit to complete the information acquired by optical absorption by detection of the param…
The dispersion and coordination of aluminium species on the surface of silica-alumina based materials are essential for controlling their catalytic activity and selectivity. Al(IV) and Al(VI) are two common coordinations of Al species in the silica network and alumina phase, respectively. Al(V) is rare in nature and was found hitherto only in the alumina phase or interfaces containing alumina, a behavior which negatively affects the dispersion, population, and accessibility of Al(V) species on the silica-alumina surface. This constraint has limited the development of silica-alumina based catal…
Predicting the Fracture Propensity of Amorphous Silica Using Molecular Dynamics Simulations and Machine Learning
Sibley School of Mechanical and Aerospace Engineering, Cornell University（康奈尔大学机械与航空航天工程学院）；Department of Engineering Mechanics, Xi’an Jiaotong University（西安交通大学工程力学系）
Proper consideration of anharmonicity is important for the calculation of the thermal conductivity. However, how the anharmonicity influences the thermal conduction in amorphous materials is still an open question. In this work, we uncover the role of anharmonicity on the thermal conductivity of amorphous silica (a-SiO2) by comparing the thermal conductivity predicted from the harmonic theory and the anharmonic theory. Moreover, we explore the effect of anharmonicity-induced frequency shift on the prediction of the thermal conductivity. It is found that the thermal conductivity calculated by t…
The passivation by diffusing H2 of silicon dangling bond defects (E' centers, induced by laser irradiation in amorphous SiO_2 (silica), is investigated in situ at several temperatures. It is found that the reaction between E' center and H_2 requires an activation energy of 0.38eV, and that its kinetics is not diffusion-limited. The results are compared with previous findings on the other fundamental paramagnetic point defect in silica, the non bridging oxygen hole center, which features completely different reaction properties with H_2. Besides, a comparison is proposed with literature data on…
This experimental PhD work deals with the generation and transformation processes of point defects induced by UV laser irradiation on amorphous silicon dioxide (silica). The investigation relies on several spectroscopic techniques used to probe the microscopic damage induced by UV laser on the material. The most innovative approach, however, is the measurement in situ of the absorption signals related to laser-induced point defects. This technique yields new information on the kinetics of defect processes, inaccessible to previous works based only on stationary measurements of laser-induced da…
We use density functional theory (DFT) to study the thermodynamic stability and migration of copper ions and small clusters embedded in amorphous silicon dioxide. We perform the calculations over an ensemble of statistically independent structures to quantify the role of the intrinsic atomic-level variability in the amorphous matrix affect the properties. The predicted formation energy of a Cu ion in the silica matrix is 2.7+/-2.4 eV, significantly lower the value for crystalline SiO2. Interestingly, we find that Cu clusters of any size are energetically favorable as compared to isolated ions;…
The mobility of O atoms at very low temperatures is not generally taken into account, despite O diffusion would add to a series of processes leading to the observed rich molecular diversity in space. We present a study of the mobility and reactivity of O atoms on an amorphous silicate surface. Our results are in the form of RAIRS and temperature-programmed desorption spectra of O2 and O3 produced via two pathways: O + O and O2 + O, investigated in a submonolayer regime and in the range of temperature between 6.5 and 30 K. All the experiments show that ozone is formed efficiently on silicate at…
We report results of molecular dynamics simulations of amorphous ice for pressures up to 22.5 kbar. The high-density amorphous ice (HDA) as prepared by pressure-induced amorphization of Ih ice at T=80 K is annealed to T=170 K at various pressures to allow for relaxation. Upon increase of pressure, relaxed amorphous ice undergoes a pronounced change of structure, ranging from the low-density amorphous ice (LDA) at p=0, through a continuum of HDA states to the limiting very high-density amorphous ice (VHDA) regime above 10 kbar. The main part of the overall structural change takes place within t…
Recent advances in our understanding of thermal transport in nanocrystalline systems are responsible for the integration of new technologies into advanced energy systems, including thermoelectric refrigeration systems and renewable energy platforms. However, there is little understanding of heat energy transport mechanisms that govern the thermal properties of disordered nanocomposites. In this work, we explore thermal transport mechanisms in disordered packings of amorphous nanoparticles with and without a polymer filling the interstices in order to quantify the impact of thermal boundary sca…
The nucleation and structure of silicon nanocrystals formed by different preparation conditions and silicon concentration (28 - 70 area %) have been studied using Transmission Electron Microscopy (TEM), Energy Filtered TEM (EFTEM) and Secondary Ion Mass Spectroscopy (SIMS). The nanocrystals were formed after heat treatment at high temperature of a sputtered 10 nm thick silicon rich oxide on 3 nm SiO$_2$ layer made by Rapid Thermal Oxidation (RTO) of silicon. Nanocrystals precipitate when the excess silicon concentration exceeds 50 area %. Below this percentage amorphous silicon nanoclusters we…
From pore collapse to crystal growth: ultrafast laser-induced stishovite formation in nanoporous silica
Université Jean Monnet, CNRS, Institut d’Optique Graduate School, Laboratoire Hubert Curien UMR 5516（让·莫兰大学，法国国家科学研究中心，高等光学研究院，于贝尔·居里实验室）；Department of Materials Science and Engineering, The Ohio State University（俄亥俄州立大学材料科学与工程系）
Diffusion limited reactions of point defects were investigated in amorphous SiO2 exposed to UV laser light. Electron spin resonance and in situ absorption measurements at room temperature evidenced the annealing of E' centers and the growth of H(II) centers both occurring in the post-irradiation stage and lasting a few hours. These transients are caused by reactions involving molecular hydrogen H2, made available by dimerization of radiolytic H0.
