Search

In studying solidification process by simulations on the atomic scale, the modeling of crystal nucleation or amorphization requires the construction of interatomic interactions that are able to reproduce the properties of both the solid and the liquid states. Taking into account rare nucleation events or structural relaxation under deep undercooling conditions requires much larger length scales and longer time scales than those achievable by ab initio molecular dynamics (AIMD). This problem is addressed by means of classical molecular dynamics simulations using a well established high dimensional neural network potential trained on a set of configurations generated by AIMD relevant for solidification phenomena. Our dataset contains various crystalline structures and liquid states at different pressures, including their time fluctuations in a wide range of temperatures. Applied to elemental aluminium, the resulting potential is shown to be efficient to reproduce the basic structural, dynamics and thermodynamic quantities in the liquid and undercooled states. Early stages of crystallization are further investigated on a much larger scale with one million atoms, allowing us to unravel features of the homogeneous nucleation mechanisms in the fcc phase at ambient pressure as well as in the bcc phase at high pressure with unprecedented accuracy close to the ab initio one. In both cases, a single step nucleation process is observed.

Ehrenfests' wind-tree model (EWTM) refers to a two-dimensional system where noninteracting point tracer particles move through a random arrangement of overlapping or nonoverlapping square-shaped scatterers. Here, extensive event-driven molecular dynamics simulations of the EWTM at different reduced scatterer densities ρ are presented. For nonoverlapping scatterers, the asymptotic motion of the tracer particles is diffusive. We compare their diffusion coefficient D, as obtained from the simulation, with that predicted by kinetic theory where D^{-1} is expanded up to the second order in the scatterer density. While at low density quantitative agreement between theory and simulation is found, we show that beyond the low-density regime deviations to the theory are associated with the emergence of a maximum in the non-Gaussian parameter at intermediate times. For the case of overlapping scatterers, in agreement with a theoretical prediction, the asymptotic motion of the tracer particles is subdiffusive, i.e., the mean-squared displacement at long times t grows like t^{1-2ρ/3}. We propose a model of the van Hove correlation function that describes the density dependence of the tracer particles' asymptotic subdiffusive transport on a quantitative level.

Extensive molecular dynamics (MD) computer simulations of an equimolar glass-forming AB mixture with large size ratio are presented. While the large A particles show a glass transition around the critical density of mode coupling theory $\rho_c$, the small B particles remain mobile with a relatively weak decrease of their self diffusion coefficient $D_{\rm B}$ with increasing density. Surprisingly, around $\rho_c$, the self-diffusion coefficient of the A particles, $D_{\rm A}$, also starts to follow a rather weak dependence on density. We show that this is due to finite-size effects that can be understood from the analysis of the collective interdiffusion dynamics., Comment: 10 pages, 8 figures

Research on soft matter and biological physics has grown tremendously in India over the past decades. In this editorial, we summarize the twenty-three research papers that were contributed to the special issue on Soft matter research in India. The papers in this issue highlight recent exciting advances in this rapidly expanding research area and include theoretical studies and numerical simulations of soft and biological systems, the synthesis and characterization of novel, functional soft materials and experimental investigations of their complex flow behaviours.

Molecular Dynamics (MD) computer simulations of a polydisperse soft-sphere model under shear are presented. Starting point for these simulations are deeply supercooled samples far below the critical temperature, $T_c$, of mode coupling theory. These samples are fully equilibrated with the aid of the swap Monte Carlo technique. For states below $T_c$, we identify a life time $\tau_{\rm lt}$ that measures the time scale on which the system can be considered as an amorphous solid. The temperature dependence of $\tau_{\rm lt}$ can be well described by an Arrhenius law. The existence of transient amorphous solid states below $T_c$ is associated with the possibility of brittle yielding, as manifested by a sharp stress drop in the stress-strain relation and shear banding. We show that brittle yielding requires on the one hand low shear rates and on the other hand, the time scale corresponding to the inverse shear rate has to be smaller or of the order of $\tau_{\rm lt}$. Both conditions can be only met for large life time $\tau_{\rm lt}$, i.e.~for states far below $T_c$., Comment: 12 pages, 11 figures

Boron oxide (B2O3) is investigated by a combination of ab initio (DFT-based) molecular dynamics (MD) simulations and classical MD simulations. From the trajectories of the ab initio MD simulation, we derive a three-body interaction potential which is used in classical MD simulations to study various structural and dynamic properties on larger time and length scales than possible in the ab initio simulations. Differences and similarities to the structure and dynamics of other network glass formers such as SiO2 and GeO2 are discussed. Moreover, various properties as obtained from the simulations are compared to those from experiments of B2O3.

Using extensive numerical simulations, we study the fluidisation process of dense amorphous materials subjected to an external shear stress, using a three-dimensional colloidal glass model. In order to disentangle possible boundary effects from finite size effects in the process of fluidisation, we implement a novel geometry-constrained protocol with periodic boundary conditions. We show that this protocol is well controlled and that the longtime fluidisation dynamics is, to a great extent, independent of the details of the protocol parameters. Our protocol, therefore, provides an ideal tool to investigate the bulk dynamics prior to yielding and to study finite size effects regarding the fluidisation process. Our study reveals the existence of precursors to fluidisation observed as a peak in the strain-rate fluctuations, that allows for a robust definition of a fluidisation time. Although the exponents in the power-law creep dynamics seem not to depend significantly on the system size, we reveal strong finite size effects for the onset of fluidisation.

The authors analyze the origin of multivalued height fluctuations, which describe the mechanical behavior of layered solids.

When systems that can undergo phase separation between two coexisting phases in the bulk are confined in thin film geometry between parallel walls, the phase behavior can be profoundly modified. These phenomena shall be described and exemplified by computer simulations of the Asakura-Oosawa model for colloid-polymer mixtures, but applications to other soft matter systems (e.g. confined polymer blends) will also be mentioned. Typically a wall will prefer one of the phases, and hence the composition of the system in the direction perpendicular to the walls will not be homogeneous. If both walls are of the same kind, this effect leads to a distortion of the phase diagram of the system in thin film geometry, in comparison with the bulk, analogous to the phenomenon of "capillary condensation" of simple fluids in thin capillaries. In the case of "competing walls", where both walls prefer different phases of the two phases coexisting in the bulk, a state with an interface parallel to the walls gets stabilized. The transition from the disordered phase to this "soft mode phase" is rounded by the finite thickness of the film and not a sharp phase transition. However, a sharp transition can occur where this interface gets localized at (one of) the walls. The relation of this interface localization transition to wetting phenomena is discussed. Finally, an outlook to related phenomena is given, such as the effects of confinement in cylindrical pores on the phase behavior, and more complicated ordering phenomena (lamellar mesophases of block copolymers or nematic phases of liquid crystals under confinement)., Comment: 25 pages, 17 figures, to be published in Soft Matter

The effect of hydrodynamic interactions (HI) on the long-time self-diffusion in quasi-two-dimensional fluids of paramagnetic colloidal particles is investigated using a combination of experiments and Brownian dynamics (BD) simulations. In the BD simulations, the direct interactions (DI) between the particles consist of a short-ranged repulsive part and a long-ranged part that is proportional to 1/r^{3}, with r the interparticle distance. By studying the equation of state, the simulations allow for the identification of the regime where the properties of the fluid are fully controlled by the long-ranged interactions, and the thermodynamic state solely depends on the dimensionless interaction strength Γ. In this regime, the radial distribution functions from the simulations are in quantitative agreement with those from the experiments for different fluid area fractions. This agreement confirms that the DI in the experiments and simulations are identical, which thus allows us to isolate the role of HI, as these are not taken into account in the BD simulations. Experiment and simulation fall onto a master curve with respect to the Γ dependence of D_{L}^{★}=D_{L}/(D_{0}Γ^{1/2}), with D_{0} the self-diffusion coefficient at infinite dilution and D_{L} the long-time self-diffusion coefficient. Our results thus show that, although HI affect the short-time self-diffusion, for a quasi-two-dimensional system with 1/r^{3} long-ranged DI, the reduced quantity D_{L}^{★} is effectively not affected by HI. Interestingly, this is in agreement with prior work on quasi-two-dimensional colloidal hard spheres.

Grandcanonical Monte Carlo simulations in combination with successive umbrella sampling are used to study interfaces in the metal-organic frameworks (MOFs) IRMOF-1 and IRMOF-8. These interf...

Molecular dynamics (MD) computer simulations are used to study the structure of hard-core Yukawa systems confined between two parallel hard walls. States around the coexistence between a fluid and a body-centered cubic (BCC) crystal are considered. In all cases a pronounced layering in the vicinity of the walls is observed. Using a thermodynamic integration scheme, we determine the wall-fluid interfacial free energy γ which is negative and monotonically decreasing with increasing bulk density of the fluid. In the case of the fluid, the layers next to the walls undergo a transition from a fluid to a hexagonal structure. This pre-freezing transition occurs well below the coexistence bulk density of the fluid. The confined BCC crystal in (111) orientation shows melted regions between crystalline face-centered cubic (FCC) layers close to the wall and the BCC bulk region.

The crystal growth kinetics as well as interfacia properties of Titanium (Ti) are studied, using molecular dynamics (MD) computer simulation. The interactions between the Ti atoms are modelled via an embedded atom method (EAM) potential. First, the free solidification method (FSM) is used to determine the melting temperature Tm at zero pressure where the transition from liquid to body-centered cubic (bcc) crystal occurs. From the simulations with the FSM, also the kinetic growth coefficients are determined for different orientations of the crystal, analyzing how the coupling to the thermostat affects the estimates of the growth coefficients. At Tm, anisotropic interfacial stiffnesses and free energies as well as kinetic growth coefficients are determined from capillary wave fluctuations. The so obtained growth coefficients from equilibrium fluctuations and without the coupling of the system to a thermostat agree well with those extracted from the FSM calculations.

The diffusion dynamics of particles in heterogeneous media is studied using particle-based simulation techniques. A special focus is placed on systems where the transport of particles at long times exhibits anomalies such as subdiffusive or superdiffusive behavior. First, a two-dimensional model system is considered containing gas particles (tracers) that diffuse through a random arrangement of pinned, disk-shaped particles. This system is similar to a classical Lorentz gas. However, different from the original Lorentz model, soft instead of hard interactions are considered and we also discuss the case where the tracer particles interact with each other. We show that the modification from hard to soft interactions strongly affects anomalous-diffusive transport at high obstacle densities. Second, non-linear active micro-rheology in a glass-forming binary Yukawa mixture is investigated, pulling single particles through a deeply supercooled state by applying a constant force. Here, we observe superdiffusion in force direction and analyze its origin. Finally, we consider the Brownian dynamics of a particle which is pulled through a two-dimensional random force field. We discuss the similarities of this model with the Lorentz gas as well as active micro-rheology in glass-forming systems.

Using a mixed classical Molecular dynamics (MD)/ab initio simulation scheme combined with a quasi-harmonic approximation, we calculate the linear thermal expansion coefficient αL(T) in vitreous silica glasses. The systems are first cooled down by classical MD simulations. Then they are structurally relaxed by ab initio DFT calculations. The vibrational properties are calculated employing the frozen phonon method, and these results are finally used to calculate the Helmholtz free energy as a function of volume. In agreement with experiments, our simulations predict that αL(T) is negative at low temperatures up to T ≈ 150 K. In this low-temperature regime, the simulation results are in quantitative agreement with experiments. To elucidate the origin of the negative thermal expansion, we analyze in detail the microscopic mode Gruneisen parameters in the system and show that the anomalous behavior of αL(T) can be related to the fact that the Gruneisen parameters for the lowest modes become negative at low temperatures – i.e., the lowest eigenfrequencies become stiffer with increasing volume.

We discuss two procedures to obtain empirical potentials from ab initio trajectories. The first method consists in adjusting the parameters of an empirical pair potential so that the radial distribution functions extracted from classical simulations using this potential match the ones extracted from the ab initio simulations. 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. With our approach we are able to obtain an empirical potential that gives a better description with respect to structural and thermodynamic properties than the potential proposed by van Beest, Kramer, and van Santen, and that has been very frequently used as a model for amorphous silica. The second method is the so-called “force matching” approach proposed by Ercolessi and Adams to obtain an empirical potential. We demonstrate that for the case of silica this method does not yield a reliable potential and discuss the likely origin for this failure.

Experiments and simulations show that when an initially defect free rigid crystal is subjected to deformation at a constant rate, irreversible plastic flow commences at the so-called {\em yield point}. The yield point is a weak function of the deformation rate, which is usually expressed as a power law with an extremely small non-universal exponent. We re-analyze a representative set of published data on nanometer sized, mostly defect free, Cu, Ni and Au crystals in the light of a recently proposed theory of yielding based on nucleation of stable stress-free regions inside the metastable rigid solid. The single relation derived here, which is {\em not} a power law, explains data covering {\em fifteen} orders of magnitude in time scales., Comment: 5 pages, 2 figures

We study active microrheology in two-dimensional (2D) magnetic networks. To this end, we use Langevin dynamics computer simulations where single non-magnetic or magnetic tracer particles are pulled through the network structures via a constant force f. Structural changes in the network around the pulled tracer particle are characterized in terms of pair correlation functions. These functions indicate that the non-magnetic tracer particles tend to strongly affect the network structure leading to the formation of channels at sufficiently high forces, while the magnetic tracer particles modify the network structure only slightly. At zero pulling force, f = 0, both non-magnetic and magnetic tracer particles are localized, i.e. they do not show diffusive behavior in the long-time limit. Nevertheless, the friction coefficient, as obtained from the steady-state velocity of the tracer particles, seems to indicate a linear-response regime at small values of f. Beyond the latter linear response regime, the diffusion dynamics of the tracer particles are anisotropic with superdiffusive behavior in force direction. This transport anomaly is investigated via van Hove correlation functions and residence time distributions.

The Soret effect, i.e., the flow of matter caused by a temperature gradient, is studied in a glass-forming binary Lennard-Jones (LJ) mixture, using nonequilibrium molecular dynamics computer simulation. The transport processes associated with this effect are thermal diffusion and interdiffusion. While interdiffusion processes exhibit a drastic slowing down when approaching the glass transition, thermal diffusion appears to be a fast process even in the glass. We show that the Soret effect becomes more pronounced in the vicinity of the glass transition, due to the decoupling between thermal diffusion and interdiffusion as well as the chemical ordering in the considered LJ mixture. This is reflected in the occurrence of large concentration gradients, nonlinear concentration profiles, and long-lived nonstationary structures.

Molecular dynamics computer simulations of a binary Lennard-Jones glass under shear are presented. The mechanical response of glassy states having different thermal histories is investigated by imposing a wide range of external shear rates, at different temperatures. The stress-strain relations exhibit an overshoot at a strain of around 0.1, marking the yielding of the glass sample and the onset of plastic flow. The amplitude of the overshoot shows a logarithmic behavior with respect to a dimensionless variable, given by the age of the sample times the shear rate. Dynamical heterogeneities having finite lifetimes, in the form of shear bands, are observed as the glass deforms under shear. By quantifying the spatial fluctuations of particle mobility, we demonstrate that such shearbanding occurs only under specific combinations of imposed shear-rate, age of glass and ambient temperature., Comment: 27 pages, 9 figures

Relaxation of shear bands in a Pd 40 Ni 40 P 20 bulk metallic glass was investigated by radiotracer diffusion allowing to determine for the first time the effective activation enthalpy of diffusion along shear bands in a deformed glass. The shear bands relax during annealing below the glass transition temperature and the diffusion enhancement reveals unexpectedly a non-monotonous, cross-over behavior. The development of shear bands and the subsequent relaxation of stresses after the shear had been switched off are characterized on microscopic to mesoscopic length scales by molecular dynamics simulation subjecting a model glass to a constant strain rate. Mean-squared displacements as well as strain maps indicate that the heterogeneity, as manifested by shear bands in the systems under shear, persist after the shear was switched off. We observe a continued relaxation of residual stresses that remain localized in regions where the shear band has been present before, although the system is – different from the macroscopic experiment – homogeneous with respect to the local density. These results indicate that even on a local scale one may expect strong dynamic heterogeneity in deformed glassy solids due to shear banding that correlates with the existence of short-circuit type diffusion on a macroscale. The results thus suggest that plastically deformed metallic glasses present poly-amorphous systems that necessitate descriptions that are analogous to multiphase materials including the presence of heterophase interfaces.

Complex rheological properties of soft disordered solids, such as colloidal gels or glasses, inspire a range of novel applications. However, the microscopic mechanisms of their response to mechanical loading are not well understood. Here, we elucidate some aspects of these mechanisms by studying a versatile model system, i.e. two-dimensional superparamagnetic colloids in a precessing magnetic field, whose structure can be tuned from a hexagonal crystal to a disordered gel network by varying the external field opening angle θ. We perform Langevin dynamics simulations subjecting these structures to a constant shear rate and observe three qualitatively different types of material response. In hexagonal crystals (θ = 0°), at a sufficiently low shear rate, plastic flow occurs via successive stress drops at which the stress releases due to the formation of dislocation defects. The gel network at θ = 48°, on the contrary, via bond rearrangement and transient shear banding evolves into a homogeneously stretched network at large strains. The latter structure remains metastable after switching off of the shear. At θ = 50°, the external shear makes the system unstable against phase separation and causes a failure of the network structure leading to the formation of hexagonal close packed clusters interconnected by particle chains. At a microcopic level, our simulations provide insight into some of the mechanisms by which strain localization as well as material failure occur in a simple gel-like network. Furthermore, we demonstrate that new stretched network structures can be generated by the application of shear.

Hard disks are one of the simplest interacting many-body model system in two dimensions (2D). Here, we present a comprehensive set of measurements of the static structure factors for quasi-2D monodisperse fluids and two different binary colloidal hard sphere mixtures: a small size ratio (SSR) system with a negligibly small negative non-additivity and a large size ratio system with a significantly larger non-additivity. We compare the experimental results for the monodisperse and SSR systems to those calculated using density functional theory (DFT) for additive mixtures. Furthermore, we determine the zero-wavevector limits of the static structure factors for the monodisperse and binary hard sphere fluids directly from an analysis of number and concentration fluctuations. For the monodisperse case, this leads to the isothermal compressibility, which agrees very well with DFT, and is consistent with the scaled particle theory equation of state for hard disks. For the binary fluids, the partial static structure factors are used to calculate the Bhatia–Thornton structure factors, and we find qualitative agreement with DFT for the SSR mixture. Finally, the zero-wavevector limits of the Bhatia–Thornton structure factors are determined and directly related to the thermodynamic factor, the dilatation factor and the isothermal compressibility.

A thermodynamic integration (TI) scheme is presented that allows us to compute the free energy of grain boundaries (GBs) in crystals from an atomistic computer simulation. Unlike previous approaches, the method can be applied at arbitrary temperatures and allows for a systematic extrapolation to the thermodynamic limit. It is applied to a $\mathrm{\ensuremath{\Sigma}}11$ GB in a face-centered-cubic Lennard-Jones crystal. At a constant density, the GB free energy shows a nonmonotonic temperature dependence with a maximum at about half the melting temperature, and the GB changes from a rigid to a rough interface with distinct finite-size scaling above this temperature.

Two-dimensional Lorentz gases formed by obstacles in the shape of circles, squares, and retroreflectors are reported to show a pronounced linear negative magnetoresistance at small magnetic fields. For circular obstacles at low number densities, our results agree with the predictions of a model based on classical retroreflection. In extension to the existing theoretical models, we find that the normalized magnetoresistance slope depends on the obstacle shape and increases as the number density of the obstacles is increased. The peaks are furthermore suppressed by in-plane magnetic fields as well as by elevated temperatures. These results suggest that classical retroreflection can form a significant contribution to the magnetoresistivity of two-dimensional Lorentz gases, while contributions from weak localization cannot be excluded, in particular for large obstacle densities.

We describe a phase transition that gives rise to structurally non-trivial states in a two-dimensional ordered network of particles connected by harmonic bonds. Monte Carlo simulations reveal that the network supports, apart from the homogeneous phase, a number of heterogeneous "pleated" phases, which can be stabilised by an external field. This field is conjugate to a global collective variable quantifying "non-affineness", i.e.~the deviation of local particle displacements from local affine deformation. In the pleated phase, stress is localised in ordered rows of pleats and eliminated from the rest of the lattice. The {\em kinetics} of the phase transition is unobservably slow in molecular dynamics simulation near coexistence, due to very large free energy barriers. When the external field is increased further to lower these barriers, the network exhibits rich dynamic behaviour: it transforms into a {\em metastable} phase with the stress now localised in a {\em disordered} arrangement of pleats. The pattern of pleats shows ageing dynamics and slow relaxation to equilibrium. Our predictions may be checked by experiments on tethered colloidal solids in dynamic laser traps., Comment: 10 pages, 8 figures

A binary mixture of superparamagnetic colloidal particles is confined between glass plates such that the large particles become fixed and provide a two-dimensional disordered matrix for the still mobile small particles, which form a fluid. By varying fluid and matrix area fractions and tuning the interactions between the superparamagnetic particles via an external magnetic field, different regions of the state diagram are explored. The mobile particles exhibit delocalized dynamics at small matrix area fractions and localized motion at high matrix area fractions, and the localization transition is rounded by the soft interactions [T. O. E. Skinner et al., Phys. Rev. Lett. 111, 128301 (2013)PRLTAO0031-900710.1103/PhysRevLett.111.128301]. Expanding on previous work, we find the dynamics of the tracers to be strongly heterogeneous and show that molecular dynamics simulations of an ideal gas confined in a fixed matrix exhibit similar behavior. The simulations show how these soft interactions make the dynamics more heterogeneous compared to the disordered Lorentz gas and lead to strong non-Gaussian fluctuations.

Crystal nucleation in the one-component metals Ni and Au is investigated using a combination of differential thermal analysis (DTA) experiments and Monte Carlo (MC) simulations. A novel experimental methodology allows to measure nucleation rates J over a range of 8 orders of magnitude. Evidence is given that these rates correspond to homogeneous nucleation. From the nucleation rates, free energy nucleation barriers ΔG ⋆ are extracted using an ansatz obtained in the framework of classical nucleation theory (CNT). The latter ansatz is rationalized by MC simulations that directly yield estimates for the temperature dependence of ΔG ⋆. The values of ΔG ⋆, as determined from the simulation, are in very good agreement with those extracted from the experiments. The simulations indicate that in the range where experiments are available the corrections to CNT are relatively small, thus justifying the application of CNT. We also discuss how the conditions for heterogeneous nucleation on a flat or structured wall can be obtained from computer simulations.

Using computer simulations, colloidal systems in different external fields are investigated. Colloid-polymer mixtures, described in terms of the Asakura-Oosawa (AO) model, are considered under strong confinement. Both in cylindrical and spherical confinement, the demixing transition of the three-dimensional AO model is rounded and, using Monte Carlo simulations, we analyze in detail the consequences of this rounding (occurrence of multi-domain states in cylindrical geometry, non-equivalence of conjugate ensembles due to different finite-size corrections in spherical geometry etc.). For the case of the AO model confined between two parallel walls, spinodal decomposition is studied using a combination of molecular dynamics simulation and the multiparticle collision dynamics method. This allows us to investigate the influence of hydrodynamic interactions on the domain growth during spinodal decomposition. For a binary glass-forming Yukawa mixture, non-linear active micro-rheology is considered, i.e. a single particle is pulled through a deeply supercooled liquid. The diffusion dynamics of the pulled particle is analyzed in terms of the van Hove correlation function. Finally, the Yukawa mixture in the glass state, confined between walls, is studied under the imposition of a uniform shear stress. Below and around the yield stress, persistent creep in the form of shear-banded structures is observed.

Using large-scale molecular dynamics simulations for a system of $10^6$ particles, the response of a dense amorphous solid to the continuous expansion of its volume is investigated. We find that the spatially uniform glassy state becomes unstable via the formation of cavities, which eventually leads to failure. By scanning through a wide range of densities and temperatures, we determine the state points at which the instability occurs and thereby provide estimates of the co-existence density of the resultant glass phase. Evidence for long-lived, inhomogeneous configurations with a negative pressure is found, where the frozen-in glass structure contains spherical cavities or a network of void space. Furthermore, we demonstrate the occurrence of hysteretic effects when the cavitated solid is compressed to regain the dense glassy state. As a result, a new glass state is obtained, the pressure of which is different from the initial one due to small density inhomogeneities that are generated by the dilation-compression cycle.

We present a systematic experimental study of the dynamic behaviour of monodisperse and bidisperse two-dimensional colloidal hard sphere fluids. We consider the diffusive behaviour of the two types of particles for systems with a variety of compositions and total area fractions. In particular, we measure the short- and long-time diffusion coefficients for both species independently. We find that the short-time self-diffusion coefficients show an approximately linear dependence on the area fraction and that the long-time self-diffusion coefficients are well described by an expression dependent upon only the area fraction and contact value of the radial distribution function. Finally, we consider the effect of composition change and find some variation in the long-time self-diffusion coefficients, which we ascribe to the complex packing effects exhibited by binary systems.

© 2015 American Physical Society. We compare experimental results from a quasi-two-dimensional colloidal hard sphere fluid to a Monte Carlo simulation of hard disks with small particle displacements. The experimental short-time self-diffusion coefficient DS scaled by the diffusion coefficient at infinite dilution, D0, strongly depends on the area fraction, pointing to significant hydrodynamic interactions at short times in the experiment, which are absent in the simulation. In contrast, the area fraction dependence of the experimental long-time self-diffusion coefficient DL/D0 is in quantitative agreement with DL/D0 obtained from the simulation. This indicates that the reduction in the particle mobility at short times due to hydrodynamic interactions does not lead to a proportional reduction in the long-time self-diffusion coefficient. Furthermore, the quantitative agreement between experiment and simulation at long times indicates that hydrodynamic interactions effectively do not affect the dependence of DL/D0 on the area fraction. In light of this, we discuss the link between structure and long-time self-diffusion in terms of a configurational excess entropy and do not find a simple exponential relation between these quantities for all fluid area fractions.

We study the behaviour of the self-intermediate scattering function and self-van Hove correlation function for quasi-two-dimensional colloidal hard sphere fluids at a range of area fractions. We compute these functions first directly from the particle coordinates and secondly from the mean squared displacement via the Gaussian approximation. This allows us to test the validity of this approximation over a range of length and time scales, where we find that the Gaussian approximation holds if the hydrodynamic limits are appropriately probed. Surprisingly, only small deviations from Gaussian behaviour are seen at intermediate times, even for dense fluids. We next consider these deviations from Gaussian behaviour firstly via the non-Gaussian parameter and secondly by considering the relaxation times of the intermediate scattering function. From these measurements we develop a scaling relation in order to directly determine the combinations of wavevectors and times at which the non-Gaussian behavior is seen. This allows for the clear identification of the hydrodynamic regimes and thus provides new insight into the crossover between long- and short-time self-diffusion.

Under external mechanical loading, glassy materials, ranging from soft matter systems to metallic alloys, often respond via formation of inhomogeneous flow patterns, during yielding. These inhomogeneities can be precursors to catastrophic failure, implying that a better understanding of their underlying mechanisms could lead to the design of smarter materials. Here, extensive molecular dynamics simulations are used to reveal the emergence of heterogeneous dynamics in a binary Lennard-Jones glass, subjected to a constant strain rate. At a critical strain, this system exhibits for all considered strain rates a transition towards the formation of a percolating cluster of mobile regions. We give evidence that this transition belongs to the universality class of directed percolation. Only at low shear rates, the percolating cluster subsequently evolves into a transient (but long-lived) shear band with a diffusive growth of its width. Finally, the steady state with a homogeneous flow pattern is reached. In the steady state, percolation transitions also do occur constantly, albeit over smaller strain intervals, to maintain the stationary plastic flow in the system.

We make use of a novel X-ray radiography method to measure chemical diffusion in capillaries in binary Al-Ni melts. Data are compared to self diffusion coefficients of Ni obtained by quasielastic neutron scattering as well as diffusion and thermodynamic data obtained by molecular dynamic simulations. Interdiffusion compared to self diffusion is enhanced with a maximum at Al40Ni60. We show that this enhancement is caused by thermodynamic forces as described by the Darken-Manning equation. In liquid Al-Ni alloys the Manning factor that is smaller than one can be attributed to collective cross correlations.

When simple or complex fluids are confined to ultrathin films or channels or other cavities of nanoscopic linear dimensions, the interplay of finite size and surface controls the phase behavior, and may lead to phase transitions rather different from the corresponding phenomena in the bulk. Monte Carlo simulation is a very suitable tool to clarify the complex behavior of such systems, since the boundary conditions providing the confinement can be controlled and arbitrarily varied, and detailed structural information on the inhomogeneous states of the considered systems is available. Examples used to illustrate these concepts include simple Ising models in pores and double-pyramid-shaped cavities with competing surface fields, where novel types of interface localization–delocalization phenomena occur accompanied by “macroscopic” fluctuations, and colloid-polymer mixtures confined in slit pores. Finite size scaling concepts are shown to be a useful tool also for such systems “in between” the dimensionalities.

In a recent work, a dense fluid flow across a nanoscopic thin plate was simulated by means of Molecular Dynamics (MD) and Lattice Boltzmann (LB) methods. It was found that in order to recover quantitative agreement with MD results, the LB simulation must be pushed down to sub–nanoscopic scales, i.e. fractions of the range of molecular interactions. In this work, we point out that in this sub–nanoscopic regime, the LB method works outside the hydrodynamic limit at the level of a single cell spacing. A quantitative comparison with the Navier–Stokes (NS) solution shows however that LB and NS results are quite similar, thereby indicating that, apart for a small region past the plate, this nanoflow is still well described by hydrodynamic equations.

Extensive grand canonical Monte Carlo simulations in combination with successive umbrella sampling are used to investigate the condensation of methane in the nanoporous crystalline material IRMOF-1. Two different types of novel condensation transitions are found, each of them ending in a critical point: (i) a fluid–fluid transition at higher densities (the analog of the liquid–gas transition in the bulk) and (ii) a phase transition at low densities on the surface of the IRMOF-1 structure. The nature of these transitions is different from the usual capillary condensation in thin films and cylindrical pores where the coexisting phases are confined in one or two of the three spatial dimensions. In contrast to that, in IRMOF-1 the different phases can be described as bulk phases that are inhomogeneous due to the presence of the metal–organic framework. As a consequence, the condensation transitions in IRMOF-1 belong to the three-dimensional (3D) Ising universality class.

Using a thermodynamic integration scheme, we compute the free energy cost per unit area, $\gamma$, of forming an interface between a crystal and a frozen structured wall, formed by particles frozen into the same equilibrium structure as the crystal. Even though the structure and potential energy of the crystalline phase in the vicinity of the wall is same as in the bulk, $\gamma$ has a non-zero value and increases with increasing density of the crystal and the wall. Investigating the effect of several interaction potentials between the particles, we observe a positive $\gamma$ at all crystalline densities if the potential is purely repulsive. For models with attractive interactions, such as the Lennard-Jones potential, a negative value for $\gamma$ is obtained at low densities., Comment: 6 pages, 5 figures

The hard sphere crystal-liquid interfacial free energy, ($\gamma_{\rm cl}$), is determined from molecular dynamics simulations using a novel thermodynamic integration (TI) scheme. The advantage of this TI scheme compared to previous methods is to successfully circumvent hysteresis effects due to the movement of the crystal-liquid interface. This is accomplished by the use of extremely short-ranged and impenetrable Gaussian flat walls which prevent the drift of the interface while imposing a negligible free-energy penalty. We find that it is crucial to analyze finite-size effects in order to obtain reliable estimates of $\gamma_{\rm cl}$ in the thermodynamic limit., Comment: 10 pages, 6 figures

Electrophoretic properties of charged colloidal suspensions are investigated using a hybrid simulation method. In this method, the colloidal particles are propagated via Newton’s equations of motion using molecular dynamics (MD), while they are coupled to a structureless solvent that is modelled by the Lattice-Boltzmann (LB) method.

The generic mechanisms of anomalous transport in porous media are investigated by computer simulations of two-dimensional model systems. In order to bridge the gap between the strongly idealized Lorentz model and realistic models of porous media, two models of increasing complexity are considered: a cherry-pit model with hard-core correlations as well as a soft-potential model. An ideal gas of tracer particles inserted into these structures is found to exhibit anomalous transport which extends up to several decades in time. Also, the self-diffusion of the tracers becomes suppressed upon increasing the density of the systems. These phenomena are attributed to an underlying percolation transition. In the soft potential model the transition is rounded, since each tracer encounters its own critical density according to its energy. Therefore, the rounding of the transition is a generic occurrence in realistic, soft systems., 10 pages, 12 figures

Effective interactions are conveniently determined from experimental or numerical data by fitting a Debye–Huckel potential with an effective charge Z ∗ and an effective electrolyte concentration c ∗ as free parameters. In this contribution we numerically solved the Poisson–Boltzmann equation to obtain the so-called renormalised charge Z PBC ∗ . For sufficiently large bare charge Z one finds a saturation of Z ∗ which scales as Z ∗ = A a / λ B , where a is the particle radius, λ B the Bjerrum length and A a proportionality factor of order (8–10). The saturation value increases with increased total micro-ion concentration and shows a shallow minimum as a function of packing fraction. In addition, the bulk shear modulus G was measured along the melting line of a colloidal crystal to obtain Z G ∗ and molecular dynamics simulations were performed within the primitive model for a pair of particles at different added salt concentration to obtain Z MD ∗ . Z PBC ∗ was then used as reference for an extensive comparison to other effective charges as obtained in the present paper and taken from literature. We observe Z G ∗ to be somewhat smaller than Z PBC ∗ and other bulk experimental effective charges, while the simulation yields Z MD ∗ ≈ Z ≫ Z PBC ∗ . These differences are discussed in the light of charge renormalisation concepts and three and many body interactions.

The (17)O NMR spectrum of CaAl(2)Si(2)O(8) glass shows two types of O sites that are not present in the crystalline material. One of these, with (17)O NMR parameters C(Q) = 2.3 MHz and delta = +20 ppm, has been assigned to a "tricluster" O, a local geometry in which the O is coordinated to three tetrahedrally coordinated atoms, either Al or Si. For crystalline CaAl(4)O(7), a tricluster site (with three Al linkages to O, i.e., OAl(3)) has been characterized experimentally, with a C(Q) of 2.5 MHz and a delta of about +40 ppm. Thus, a C(Q) value of 2.5 MHz or less seems to be a characteristic of such sites, although they may show a range of delta values. However, several different quantum chemical cluster calculations employing energy-optimized geometries for various tricluster species have given C(Q) values considerably larger than that seen experimentally in the CaAl(2)Si(2)O(8) glass (with minimum C(Q) values of 3.0 MHz even for all Al species). We have recently shown that for edge-sharing geometries, in which the tricluster O atoms participate in "two-membered rings" of composition Al(2)O(2), the calculated C(Q) values are considerably lower, in the range identified in the glass. However, such two-membered ring geometries had been observed only in crystalline inorganic alumoxanes. Ab initio MD calculations on related compositions, such as the calcium aluminosilicate, CAS, (CaO)(0.21)(Al(2)O(3))(0.12)(SiO(2))(0.67), show a small percentage of O triclusters, but none in two-membered rings of the Al(2)O(2) type, and the calculated C(Q) values for the triclusters that do exist are higher than seen in the original experiments on CaAl(2)Si(2)O(8) glass and not significantly different from those for two-coordinate O in Si-O-Al sites. However, a classical MD simulation of the structure of glassy aluminum silicate AS2, (Al(2)O(3))2(SiO(2)), gave a predominance of O triclusters within two-membered rings, with structures much like those seen in the alumoxanes. We have now calculated (17)O nuclear quadrupole coupling constants and NMR shielding values for clusters extracted from these simulations, using standard quantum chemical methods. The calculated C(Q) values for these O triclusters are now in the range observed experimentally in the CaAl(2)Si(2)O(8) glass (around 2.3-2.6 MHz) when the tricluster O is surrounded by three Al, two of which are part of an Al(2)O(2) ring. This supports the experimentalists' contention that such tricluster O species do exist and have been seen by (17)O NMR.

Structural and dynamic properties of silicate melts and glasses (SiO 2 and its mixtures with Na 2 O and Al 2 O 3 ) are derived from Molecular Dynamics simulations and compared to pertinent experimental data. It is shown that these mixtures exhibit additional intermediate order as compared to pure silica, where the characteristic length scales stem from the tetrahedral network structure. While sodium ions show much faster diffusion through percolating channels than the silicon and oxygen ions forming the surrounding network, aluminium ions are incorporated into the network (leading to tricluster formation) and do not show such an enhanced mobility.

A Lennard–Jones model of a binary (AB) dense liquid with a symmetrical miscibility gap is investigated by means of computer simulation methods. Semigrand-canonical Monte Carlo simulations yield the phase diagram in the T–x plane (T: temperature, x: concentration of A or B particles), as well as equilibrated configurations at coexistence. Then, we undertake molecular dynamics simulations which use these configurations to determine static properties (isothermal compressibility κ T , and concentration susceptibility χ), as well as the shear and bulk viscosities ηs and ηB, respectively. The latter quantities are calculated along a path approaching the coexistence line from high temperatures in the one-phase region and ending at a state at the coexistence line about 15% below the critical point. We find that κ T and χ increase significantly near the coexistence line, reflecting the vicinity of the critical point. Whereas η s exhibits a weak temperature-dependence, ηB increases significantly near the coexistenc...

We present the results of large-scale computer simulations in order to discuss the structural and dynamic properties of sodium silicate melts with the compositions (Na2O)2(SiO2) (NS2) and (Na2O)20(SiO2) (NS20). We show that, compared to silica (SiO2), these systems exhibit additional intermediate range order on intermediate length scales that stem from the tetrahedral network structure. By means of intermediate-scattering functions, we characterize the dynamics of sodium in the system under consideration. Whereas in NS2 the incoherent scattering functions for Na decay much faster to zero than the coherent ones for Na–Na, in NS20 this different behaviour of the incoherent and coherent functions is not very pronounced. On the other hand, the incoherent functions of the two systems share a very peculiar feature: their long-time decay can be described by a Kohlrausch law with a constant exponent β for q_{th}$>q > qth where qth is significantly below the location of the main peak in the static structure factor for the Na–Na correlations.

We used quasielastic neutron scattering and molecular dynamics simulations in order to study the interplay of intermediate range order, atomic dynamics and properties of mass transport in sodium silicate melts. Our results show that the sodium ions align in sodium rich channels that disrupt the Si-O structure and that form a percolation network. The sodium ions diffuse along these channels in a relatively immobile Si-O network. The diffusion via these channels results in a decoupling of incoherent from coherent correlations of the sodium relaxation, as evidenced by simulation and experiment. A characteristic length scale for this channel structure is marked by prepeaks in the elastic structure factors at about q = 0.9 A-1, corresponding to length scales of the order of 7 A.