arXiv subjects

Walter Kob

Publications and source records attributed to Walter Kob.

At least 55 records · Page 3Linked to original sources

arXiv2020

Revealing the three-dimensional structure of liquids using four-point correlation functions

Disordered systems like liquids, gels, glasses, or granular materials are not only ubiquitous in daily life and in industrial applications but they are also crucial for the mechanical stability of cells or the transport of chemical and biological agents in living organisms. Despite the importance of these systems, their microscopic structure is understood only on a rudimentary level, thus in stark contrast to the case of gases and crystals. Since scattering experiments and analytical calculations usually give only structural information that is spherically averaged, the three dimensional (3D) structure of disordered systems is basically unknown. Here we introduce a simple method that allows to probe the 3D structure of such systems. Using computer simulations we find that hard-sphere-like liquids have on intermediate and large scales an intricate structural order given by alternating layers with icosahedral and dodecahedral symmetries, while open network liquids like silica have a structural order with tetrahedral symmetry. These results show that liquids have a highly non-trivial 3D structure and that this structural information is encoded in non-standard correlation functions.

cond-mat.dis-nn↗

arXiv2020

Structure and vibrational properties of sodium silicate glass surfaces

Using molecular dynamics simulations we investigate the dependence of the structural and vibrational properties of the surfaces of sodo-silicate glasses on the sodium content as well as the nature of the surface. Two types of glass surfaces are considered: A melt-formed surface (MS) in which a liquid with a free surface has been cooled down into the glass phase and a fracture surface (FS) obtained by tensile loading of a glass sample. We find that the MS is more abundant in Na and non-bridging oxygen atoms than the FS and the bulk glass, whereas the FS has higher concentration of structural defects such as two-membered rings and under-coordinated Si than the MS. We associate these structural differences to the production histories of the glasses and the mobility of the Na ions. It is also found that for Na-poor systems the fluctuations in composition and local atomic charge density decay with a power-law as a function of distance from the surface while Na-rich systems show an exponential decay with a typical decay length of $\approx2.3$~Å. The vibrational density of states shows that the presence of the surfaces leads to a decrease of the characteristic frequencies in the system. The two-membered rings give rise to a pronounce band at $\approx880$~cm$^{-1}$ which is in good agreement experimental observations.

cond-mat.dis-nn↗

arXiv2019

New interaction potentials for borate glasses with mixed network formers

We adapt and apply a recently developed optimization scheme used to obtain effective potentials for aluminosilicate glasses to include the network former boron into the interaction parameter set. As input data for the optimization, we used the radial distribution functions of the liquid at high temperature generated by ab initio molecular dynamics simulations, and density, coordination and elastic modulus of glass at room temperature from experiments. The new interaction potentials are shown to reproduce reliably the structure, coordination and mechanical properties over a wide range of compositions for binary alkali borates. Furthermore, the transferability of these new interaction parameters allows mixing to reliably reproduce properties of various boroaluminate and borosilicate glasses.

physics.comp-ph↗

arXiv2019

Characterizing the mesh size of polymer solutions via the pore size distribution

In order to characterize the geometrical mesh size $ξ$, we simulate a solution of coarse-grained polymers with densities ranging from the dilute to the concentrated regime and for different chain lengths. Conventional ways to estimate $ξ$ rely either on scaling assumptions which give $ξ$ only up to an unknown multiplicative factor, or on measurements of the monomer density fluctuation correlation length $ξ_c$. We determine $ξ_c$ from the monomer structure factor and from the radial distribution function, and find that the identification $ξ=ξ_c$ is not justified outside of the semidilute regime. In order to better characterize $ξ$, we compute the pore size distribution (PSD) following two different definitions, one by Torquato et al. (Ref.1) and one by Gubbins et al. (Ref.2). We show that the mean values of the two distributions, $\langle r \rangle_T$ and $\langle r \rangle_G$, both display the behavior predicted for $ξ$ by scaling theory, and argue that $ξ$ can be identified with either one of these quantities. This identification allows to interpret the PSD as the distribution of mesh sizes, a quantity which conventional methods cannot access. Finally, we show that it is possible to map a polymer solution on a system of hard or overlapping spheres, for which Torquato's PSD can be computed analytically and reproduces accurately the PSD of the solution. We give an expression that allows $\langle r \rangle_T$ to be estimated with great accuracy in the semidilute regime by knowing only the radius of gyration and the density of the polymers.

cond-mat.soft↗

arXiv2019

Addition to Structure and dynamics of a polymer-nanoparticle composite: Effect of nanoparticle size and volume fraction

In our previous publication (Ref. 1) we have shown that the data for the normalized diffusion coefficient of the polymers, $D_p/D_{p0}$, falls on a master curve when plotted as a function of $h/λ_d$, where $h$ is the mean interparticle distance and $λ_d$ is a dynamic length scale. In the present note we show that also the normalized diffusion coefficient of the nanoparticles, $D_N/D_{N0}$, collapses on a master curve when plotted as a function of $h/R_h$, where $R_h$ is the hydrodynamic radius of the nanoparticles.

cond-mat.soft↗

arXiv2019

Basis Glass States: New Insights from the Potential Energy Landscape

Using the potential energy landscape formalism we show that, in the temperature range in which the dynamics of a glass forming system is thermally activated, there exists a unique set of "basis glass states" each of which is confined to a single metabasin of the energy landscape of a glass forming system. These basis glass states tile the entire configuration space of the system, exhibit only secondary relaxation and are solid-like. Any macroscopic state of the system (whether liquid or glass) can be represented as a superposition of basis glass states and can be described by a probability distribution over these states. During cooling of a liquid from a high temperature, the probability distribution freezes at sufficiently low temperatures describing the process of liquid to glass transition. The time evolution of the probability distribution towards the equilibrium distribution during subsequent aging describes the primary relaxation of a glass.

cond-mat.dis-nn↗

arXiv2019

On the Structure of Liquids: More order than expected

Disordered systems like liquids, gels, glasses, or granular materials are not only ubiquitous in daily life and in industrial applications but they are also crucial for the mechanical stability of cells or the transport of chemical and biological agents in living organisms [1-3]. Despite the importance of these systems, their microscopic structure is understood only on a rudimentary level, thus in stark contrast to the case of gases and crystals [1,4]. Experimental and theoretical investigations indicate that disordered systems have a structural order on the length scale of a few particle diameters but which then quickly vanishes at larger distances [5]. This conclusion is, however, based mainly on the behavior of two-point correlation functions such as the static structure factor or the radial distribution function [5.6]. Whether or not disordered systems have an order that extents to larger length scales is therefore a highly important question that is still open [7-10]. Here we use computer simulations to show that liquids have an intricate structural order given by alternating layers with icosahedral and dodecahedral symmetries and which extends to surprisingly large distances. We show that the temperature dependence of the corresponding length scale can be detected in the static structure factor, making it directly accessible to scattering experiments. These results, obtained by a novel type of four point correlation function that probes directly the particle density in three dimensions, show that liquids are far more ordered than envisaged so far but that this structural information is encoded in non-standard correlation functions.

cond-mat.dis-nn↗

arXiv2019

Probing the Local Response of Glass-forming Liquids by Laser Excitations

The glass is a disordered solid that processes distinct dynamical and elastic properties compared with crystal. How heterogeneous glassy materials can be and to what extent dynamics is encoded with structure and elasticity are long-standing puzzles in glass science. In this experiment, we probed the responses of binary colloidal glasses towards the excitations induced by highly focused laser pulses. We observed very similar excitation patterns when the laser was repeated in the linear region; directly proving that the dynamical heterogeneity is strongly encoded with structure. In the non-linear region, we identified a non-monotonic dynamical length scale as a function of area fraction, resulting from the non-monotonic coupling of momentum transfer in radial and orthogonal directions. Surprisingly, the excitation size and radius of gyration conformed to a universal scaling relation that covered both linear and non-linear regions. Our experiments offered a new strategy of actively probing the response of glassy materials on the microscopic level.

cond-mat.soft↗

arXiv2018

Ideal glass states are not purely vibrational: Insight from randomly pinned glasses

We use computer simulations to probe the thermodynamic and dynamic properties of a glass-former that undergoes an ideal glass-transition because of the presence of randomly pinned particles. We find that even deep in the equilibrium glass state the system relaxes to some extent because of the presence of localized excitations that allow the system to access different inherent structures, giving thus rise to a non-trivial contribution to the entropy. By calculating with high accuracy the vibrational part of the entropy, we show that also in the equilibrium glass state thermodynamics and dynamics give a coherent picture and that glasses should not be seen as a disordered solid in which the particles undergo just vibrational motion but instead as a system with a highly nonlinear internal dynamics.

cond-mat.dis-nn↗

arXiv2018

New interaction potentials for alkali and alkaline-earth aluminosilicate glasses

We apply a recently developed optimization scheme to obtain effective potentials for alkali and alkaline-earth aluminosilicate glasses that contains lithium, sodium, potassium, or calcium as modifiers. As input data for the optimization, we used the radial distribution functions of the liquid at high temperature generated by means of ab initio molecular dynamics simulations and density and elastic modulus of glass at room temperature from experiments. The new interaction potentials are able to reproduce reliably the structure and various mechanical and vibrational properties over a wide range of compositions for binary silicates. We have tested these potentials for various ternary systems and find that they are transferable and can be mixed, thus allowing to reproduce and predict the structure and properties of multi-component glasses.

physics.comp-ph↗

arXiv2018

Structure and dynamics of a polymer-nanoparticle composite: Effect of nanoparticle size and volume fraction

We use molecular dynamics simulations to study a semidilute, unentangled polymer solution containing well dispersed, weakly attractive nanoparticles (NP) of size ($σ_N$) smaller than the polymer radius of gyration $R_g$. We find that if $σ_N$ is larger than the monomer size the polymers swell, while smaller NPs cause chain contraction. The diffusion coefficient of polymer chains ($D_p$) and NPs ($D_N$) decreases if the volume fraction $ϕ_N$ is increased. The decrease of $D_p$ can be well described in terms of a confinement parameter, while $D_N$ shows a more complex dependence on $σ_N$, which results from an interplay between energetic and entropic effects. When $ϕ_N$ exceeds a $σ_N$-dependent value, the NPs are no longer well dispersed and $D_N$ and $D_p$ increase if $ϕ_N$ is increased.

cond-mat.soft↗

arXiv2018

Stretched and compressed exponentials in the relaxation dynamics of a metallic glass-forming melt

The relaxation dynamics of glass-forming systems shows a multitude of features that are absent in normal liquids, such as non-exponential relaxation and a strong temperature-dependence of the relaxation time. Connecting these dynamic properties to the microscopic structure of the system is very challenging because of the presence of the structural disorder. Here we use computer simulations of a metallic glass-former to establish such a connection. By probing the temperature and wave-vector dependence of the intermediate scattering function we find that the relaxation dynamics of the glassy melt is directly related to the local arrangement of icosahedral structures: Isolated icosahedra give rise to a flow-like stretched exponential relaxation whereas clusters of icosahedra lead to a compressed exponential relaxation that is reminiscent to the one found in a solid. Our results show that in metallic glass-formers these two types of relaxation processes can coexist and give rise to a surprisingly complex dynamics, insight that will allow to get a deeper understanding of the outstanding mechanical properties of metallic glasses.

cond-mat.dis-nn↗

arXiv2018

Structural and Topological Nature of Plasticity in Sheared Granular Materials

Upon mechanical loading, granular materials yield and undergo plastic deformation. The nature of plastic deformation is essential for the development of the macroscopic constitutive models and the understanding of shear band formation. However, we still do not fully understand the microscopic nature of plastic deformation in disordered granular materials. Here we used synchrotron X-ray tomography technique to track the structural evolutions of three-dimensional granular materials under shear. We establish that highly distorted coplanar tetrahedra are the structural defects responsible for microscopic plasticity in disordered granular packings. The elementary plastic events occur through flip events which correspond to a neighbor switching process among these coplanar tetrahedra (or equivalently as the rotation motion of 4-ring disclinations). These events are discrete in space and possess specific orientations with the principal stress direction.

cond-mat.soft↗

arXiv2018

Dynamic and thermodynamic crossover scenarios in the Kob-Andersen mixture: Insights from multi-CPU and multi-GPU simulations

The physical behavior of glass-forming liquids presents complex features of both dynamic and thermodynamic nature. Some studies indicate the presence of thermodynamic anomalies and of crossovers in the dynamic properties, but their origin and degree of universality is difficult to assess. Moreover, conventional simulations are barely able to cover the range of temperatures at which these crossovers usually occur. To address these issues, we simulate the Kob-Andersen Lennard-Jones mixture using efficient protocols based on multi-CPU and multi-GPU parallel tempering. Our setup enables us to probe the thermodynamics and dynamics of the liquid at equilibrium well below the critical temperature of mode-coupling theory, $T_{\rm MCT} = 0.435$. We find that below $T=0.4$ the analysis is hampered by partial crystallization of the metastable liquid, which nucleates extended regions populated by large particles arranged in an fcc structure. By filtering out crystalline samples, we reveal that the specific heat grows in a regular manner down to $T=0.38$. Possible thermodynamic anomalies suggested by previous studies can thus occur only in a region of the phase diagram where the system is highly metastable. Using the equilibrium configurations obtained from the parallel tempering simulations, we perform molecular dynamics and Monte Carlo simulations to probe the equilibrium dynamics down to $T=0.4$. A temperature-derivative analysis of the relaxation time and diffusion data allows us to assess different dynamic scenarios around $T_{\rm MCT}$. Hints of a dynamic crossover come from analysis of the four-point dynamic susceptibility. Finally, we discuss possible future numerical strategies to clarify the nature of crossover phenomena in glass-forming liquids.

cond-mat.stat-mech↗

arXiv2018

New optimization scheme to obtain interaction potentials for oxide glasses

We propose a new scheme to parameterize effective potentials that can be used to simulate atomic systems such as oxide glasses. As input data for the optimization, we use the radial distribution functions of the liquid and the vibrational density of state of the glass, both obtained from ab-initio simulations, as well as experimental data on the pressure dependence of the density of the glass. For the case of silica, we find that this new scheme facilitates finding pair potentials that are significantly more accurate than previous ones even if the functional form is the same, thus demonstrating that even simple two-body potentials can be superior to more complex three-body potentials. We have tested the new potential by calculating the pressure dependence of the elastic moduli and find a good agreement with the corresponding experimental data.

cond-mat.mtrl-sci↗

arXiv2018

Translational and rotational dynamical heterogeneities in granular systems

We use X-ray tomography to investigate the translational and rotational dynamical heterogeneities of a three dimensional hard ellipsoids granular packing driven by oscillatory shear. We find that particles which translate quickly form clusters with a size distribution given by a power-law with an exponent that is independent of the strain amplitude. Identical behavior is found for particles that are translating slowly, rotating quickly, or rotating slowly. The geometrical properties of these four different types of clusters are the same as those of random clusters. Different cluster types are considerably correlated/anticorrelated, indicating a significant coupling between translational and rotational degrees of freedom. Surprisingly these clusters are formed already at time scales that are much shorter than the $α-$relaxation time, in stark contrast to the behavior found in glass-forming systems.

cond-mat.dis-nn↗

arXiv2017

Granular materials flow like complex fluids

Granular materials such as sand, powders, foams etc. are ubiquitous in our daily life, as well as in industrial and geotechnical applications. Although these disordered systems form stable structures if unperturbed, in practice they do relax because of the presence of unavoidable external influences such as tapping or shear. Often it is tacitly assumed that for granular systems this relaxation dynamics is similar to the one of thermal glass-formers, but in fact experimental difficulties have so far prevented to determine the dynamic properties of three dimensional granular systems on the particle level. This lack of experimental data, combined with the fact that in these systems the motion of the particles involves friction, makes it very challenging to come up with an accurate description of their relaxation dynamics. Here we use X-ray tomography to determine the microscopic relaxation dynamics of hard granular ellipsoids that are subject to an oscillatory shear. We find that the distribution function of the particle displacement can be described by a Gumbel law with a shape parameter that is independent of time and the strain amplitude $γ$. Despite this universality, the mean squared displacement of a tagged particle shows power-laws as a function of time with an exponent that depends on $γ$ and the time interval considered. We argue that these results are directly related to the existence of the microscopic relaxation mechanisms that involve friction and memory effects. These observations demonstrate that on the particle level the dynamical behavior of granular systems is qualitatively different from the one of thermal glass-formers and instead more similar to the one of complex fluids. Thus we conclude that granular materials can relax even when the driving is weak, an insight which impacts our understanding of the nature of granular solids.

cond-mat.soft↗

arXiv2017

Structuring polymer gels via catalytic reactions

We use computer simulations to investigate how a catalytic reaction in a polymer sol can induce the formation of a polymer gel. To this aim we consider a solution of homopolymers in which freely-diffusing catalysts convert the originally repulsive A monomers into attractive B ones. We find that at low temperatures this reaction transforms the polymer solution into a physical gel that has a remarkably regular mesostructure in the form of a cluster phase, absent in the usual homopolymer gels obtained by a quench in temperature. We investigate how this microstructuring depends on catalyst concentration, temperature, and polymer density and show that the dynamics for its formation can be understood in a semi-quantitative manner using the interaction potentials between the particles as input. The structuring of the copolymers and the AB sequences resulting from the reactions can be discussed in the context of the phase behaviour of correlated random copolymers. The location of the spinodal line as found in our simulations is consistent with analytical predictions. Finally, we show that the observed structuring depends not only on the chemical distribution of the A and B monomers but also on the mode of formation of this distribution.

cond-mat.soft↗