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Novel structural transitions of solvent-free oligomer-grafted nanoparticles are investigated by using molecular dynamics simulations of a coarse-grained bead-spring model. Variations in core size and grafting density lead to self-assembly of the nanoparticles into a variety of distinct structures. At the boundaries between different structures, the nanoparticle systems undergo thermoreversible transitions. This structural behavior, which has not been previously reported, deviates significantly from that of simple liquids. The reversible nature of these transitions in solvent-free conditions offers new ways to control self-assembly of nanoparticles at experimentally accessible conditions. [ABSTRACT FROM AUTHOR]

Structural features of phase-separated athermal colloid-polymer mixtures in the so-called "protein limit," where polymer chain dimensions exceed those of the colloid, are investigated using grand canonical Monte Carlo simulations on a fine lattice. Previous work [N. A. Mahynski et al., Phys. Rev. E 85, 051402 (2012)] has shown that this model accurately captures the phase behavior of experimental systems, and that colloids with sufficiently small diameters, σc, relative to that of the monomeric segments, σs, phase separate more readily than their large-diameter counterparts. In the present study, we directly connect colloid and polymer structure with their phase behavior by investigating these solutions along their binodal curves; we also explore the role of colloid surface curvature in destabilizing such solutions. Our findings suggest that simple consideration of an additional depletion radius, on the order of the σs, leads to a quantitatively accurate prediction of the division between stable and unstable ranges of d = σs/σc. We compare these results to continuum models with different bonding potentials between monomer segments in order to elucidate the significance of the lattice model's bond fluctuations and inherently coarse colloid surface. In a number of cases, the continuum models deviate both qualitatively and quantitatively from the lattice results, but the binodals of the continuum models are presently not known, making a strong conclusion about these differences impossible. [ABSTRACT FROM AUTHOR]

Grand canonical Monte Carlo and histogram reweighting techniques are used to study the fluid-phase behavior of an athermal system of colloids and nonadsorbing polymers on a fine lattice in the "protein limit," where polymer dimensions exceed those of the colloids. The main parameters are the chains' radius of gyration, Rg, the diameter of the colloids, &sgr;c, and the monomer diameter, &sgr;c. The phase behavior is controlled by the macroscopic size ratio, qr = 2Rg/&sgr;c, and the microscopic size ratio, d = &sgr;s/&sgr;c. The latter ratio is found to play a significant role in determining the critical monomer concentration for qr ≲ 4 and the critical colloid density for all chain lengths. However, the critical (osmotic) pressure is independent of the microscopic size ratio at all macroscopic size ratios studied. Quantitative agreement is observed between our simulation results and experimental data. We scale our results based on the polymer correlation length, which has previously been suggested to universally collapse these binodals [Bolhuis et al, Phys. Rev. Lett. 90, 068304 (2003); Fleer and Tuinier, Phys. Rev. E 76, 041802 (2007)]. While the density binodals exhibit universal characteristics along the low-colloid-density branch, such features are not present in the corresponding high-density phase. However, pressure binodals do collapse nicely under such a scaling, even far from the critical point, which allows us to produce a binodal curve whose shape is independent of either size ratio. [ABSTRACT FROM AUTHOR]

A new modified embedded-atom method (MEAM) force field is developed for liquid tin. Starting from the Ravelo and Baskes force field [Phys. Rev. Lett. 79, 2482 (1997)], the parameters are adjusted using a simulated annealing optimization procedure in order to obtain better agreement with liquid-phase data. The predictive capabilities of the new model and the Ravelo and Baskes force field are evaluated using molecular dynamics by comparing to a wide range of first-principles and experimental data. The quantities studied include crystal properties (cohesive energy, bulk modulus, equilibrium density, and lattice constant of various crystal structures), melting temperature, liquid structure, liquid density, self-diffusivity, viscosity, and vapor-liquid surface tension. It is shown that although the Ravelo and Baskes force field generally gives better agreement with the properties related to the solid phases of tin, the new MEAM force field gives better agreement with liquid tin properties. [ABSTRACT FROM AUTHOR]

The dielectric permittivity of salt water decreases on dissolving more salt. For nearly a century, this phenomenon has been explained by invoking saturation in the dielectric response of the solvent water molecules. Herein, we employ an advanced deep neural network (DNN), built using data from density functional theory, to study the dielectric permittivity of sodium chloride solutions. Notably, the decrease in the dielectric permittivity as a function of concentration, computed using the DNN approach, agrees well with experiments. Detailed analysis of the computations reveals that the dominant effect, caused by the intrusion of ionic hydration shells into the solvent hydrogen-bond network, is the disruption of dipolar correlations among water molecules. Accordingly, the observed decrease in the dielectric permittivity is mostly due to increasing suppression of the collective response of solvent waters.

A long-standing question in water research is the possibility that supercooled liquid water can undergo a liquid-liquid phase transition (LLT) into high- and low-density liquids. We used several complementary molecular simulation techniques to evaluate the possibility of an LLT in an ab initio neural network model of water trained on density functional theory calculations with the SCAN exchange correlation functional. We conclusively show the existence of a first-order LLT and an associated critical point in the SCAN description of water, representing the first definitive computational evidence for an LLT in water from first principles.

Telechelic star polymers are macromolecules with functionalized, mutually attractive end groups. We employ computer simulations on a lattice to investigate the phase behavior of trifunctional telechelic stars as a function of the fraction lambda of attractive terminal monomers. We find macrophase separation that disappears at some value 0.4

Grand-canonical simulations designed to resolve critical universality classes are reported for z:1 hard-core electrolyte models with diameter ratios lambda=a+/a- less than or approximately equal 6. For z=1 Ising-type behavior prevails. Unbiased estimates of Tc(lambda) are within 1% of previous (biased) estimates but the critical densities are approximately 5% lower. Ising character is also established for the 2:1 and 3:1 equisized models, along with critical amplitudes and improved Tc estimates. For z=3, however, strong finite-size effects reduce the confidence level although classical and O (n>or=3) criticality are excluded.

Using molecular dynamics simulations, we show that sheared solutions of cylindrical micelle-forming amphiphiles behave very differently under extreme confinement as compared to the bulk. When confined to ultrathin films, the self-assembled cylindrical micelles roll along the shearing direction and align parallel to each other with their axes along the vorticity direction, as opposed to aligning parallel to the shearing direction in the bulk. It is shown that this new "log-rolling" phase arises due to a strong coupling between the rotational degree of freedom of the micelles and the steady sliding motion of the confining surfaces. We examine the microscopic mechanism of the log-rolling phenomenon and also discuss its dependence on the segregation strength and length of the amphiphile, the shear rate, and the film thickness.

The phase behavior of the lattice restricted primitive model (RPM) for ionic systems with additional short-range nearest neighbor (NN) repulsive interactions has been studied by grand canonical Monte Carlo simulations. We obtain a rich phase behavior as the NN strength is varied. In particular, the phase diagram is very similar to that of the continuum RPM for high NN strength. Specifically, we have found both gas-liquid phase separation, with associated Ising critical point, and a first-order liquid-solid transition. We discuss how the line of continuous order-disorder transitions present for the low NN strength changes into continuum-space behavior as one increases the NN strength and compare our findings with recent theoretical results by Ciach and Stell [Phys. Rev. Lett. 91, 060601 (2003)].

The behavior of confined cylindrical micelle-forming surfactants under the influence of shear has been investigated using Monte Carlo simulations. The surfactants are modeled as coarse-grained lattice polymers, while the Monte Carlo shear flow is implemented with an externally imposed potential energy field which induces a linear drag velocity on the surfactants. It is shown that, in the absence of shear, cylindrical micelles confined within a monolayer coarsen gradually with Monte Carlo "time" t , the persistence length of the micelles scaling as t(0.24) , in agreement with the scaling obtained experimentally. Under the imposition of shear, the micelles within a monolayer align parallel to the direction of shear, as observed experimentally. Micelles confined within thicker films also align parallel to each other with a hexagonal packing under shear, but assume a finite tilt with respect to the velocity vector within the velocity-velocity gradient plane. We propose a mechanism for this shear-induced alignment of micelles based on breaking up of micelles aligned perpendicular to the shear and their reformation and subsequent growth in the shear direction. It is observed that there exists a "window" of shear rates within which such alignment occurs. A simple theory proposed to explain the above behavior is in good agreement with simulation results. A comparison of simulated and experimental self-diffusivities yields a physical time scale for Monte Carlo moves, which enables an assessment of the physical shear rates employed in our Monte Carlo simulations.

We formally extend the energy landscape approach for the thermodynamics of liquids to account for saddle points. By considering the extensive nature of macroscopic potential energies, we derive the scaling behavior of saddles with system size, as well as several approximations for the properties of low-order saddles (i.e., those with only a few unstable directions). We then cast the canonical partition function in a saddle-explicit form and develop, for the first time, a rigorous energy landscape approach capable of reproducing trends observed in simulations, in particular, the temperature dependence of the energy and fractional order of sampled saddles.

The phase behavior of ionic fluids on simple cubic and tetragonal (anisotropic) lattices has been studied by grand canonical Monte Carlo simulations. Systems with both the true lattice Coulombic potential and continuous-space 1/r electrostatic interactions have been investigated. At all degrees of anisotropy, only coexistence between a disordered low-density phase and an ordered high-density phase with the structure similar to ionic crystal was found, in contrast to recent theoretical predictions. Tricritical parameters were determined to be increasing functions of anisotropy parameters which is consistent with theoretical calculations based on the Debye-Hückel approach. At large anisotropies a two-dimensional-like behavior is observed, from which we estimated the dimensionless tricritical temperature and density for the two-dimensional square lattice electrolyte to be T*(tri)=0.14 and rho*(tri)=0.70.

The role of charges in determining the water solubility of polyelectrolytes, a question of considerable relevance to biology, is currently unresolved. We use computer simulations to study the purely Coulombic phase separation of flexible polyelectrolytes with monovalent counterions in an athermal solvent. In agreement with recent theories we find that the critical temperature for this transition increases with chain length, but that the critical density remains unchanged. We therefore stress that the phase behavior of polyelectrolytes is qualitatively different from uncharged polymers, where the critical density decreases towards zero for long chains.

We present a rigorous derivation for off-lattice implementations of the so-called "random-walk" algorithm recently introduced by Wang and Landau [Phys. Rev. Lett. 86, 2050 (2001)]. Originally developed for discrete systems, the algorithm samples configurations according to their inverse density of states using Monte Carlo moves; the estimate for the density of states is refined at each simulation step and is ultimately used to calculate thermodynamic properties. We present an implementation for atomic systems based on a rigorous separation of kinetic and configurational contributions to the density of states. By constructing a "uniform" ensemble for configurational degrees of freedom-in which all potential energies, volumes, and numbers of particles are equally probable-we establish a framework for the correct implementation of simulation acceptance criteria and calculation of thermodynamic averages in the continuum case. To demonstrate the generality of our approach, we perform sample calculations for the Lennard-Jones fluid using two implementation variants and in both cases find good agreement with established literature values for the vapor-liquid coexistence locus.

The present investigation examines the relationship between structural order, diffusivity anomalies, and density anomalies in liquid silica by means of molecular dynamics simulations. We use previously defined orientational and translational order parameters to quantify local structural order in atomic configurations. Extensive simulations are performed at different state points to measure structural order, diffusivity, and thermodynamic properties. It is found that silica shares many trends recently reported for water [J. R. Errington and P. G. Debenedetti, Nature 409, 318 (2001)]. At intermediate densities, the distribution of local orientational order is bimodal. At fixed temperature, order parameter extrema occur upon compression: a maximum in orientational order followed by a minimum in translational order. Unlike water, however, silica's translational order parameter minimum is broad, and there is no range of thermodynamic conditions where both parameters are strictly coupled. Furthermore, the temperature-density regime where both structural order parameters decrease upon isothermal compression (the structurally anomalous regime) does not encompass the region of diffusivity anomalies, as was the case for water.

The 1:1 equisized hard-sphere electrolyte or restricted primitive model has been simulated via grand-canonical fine-discretization Monte Carlo. Newly devised unbiased finite-size extrapolation methods using loci in the temperature-density or (T,rho) plane of isothermal rho(2-k) vs pressure inflections, of Q identical with(2)/ maxima, and of canonical and C(V) criticality, yield estimates of (T(c),rho(c)) to +/-(0.04,3)%. Extrapolated exponents and Q ratio are (gamma,nu,Q(c)) = [1.24(3), 0.63(3); 0.624(2)], which support Ising (n = 1) behavior with (1.23(9), 0.630(3); 0.623(6)), but exclude classical, XY (n = 2), self-avoiding walk (n = 0), and n = 1 criticality with potentials varphi(r)>Phi/r(4.9) when r-->infinity.

Critical temperatures, T(c), densities, rho(c), and coexistence curves for 2:1 and 3:1 hard-core model electrolytes have been found by fine-discretization Monte Carlo simulation. The size ratio of + and - ions strongly affects T(c) and rho(c); the trends contradict most current theories. Large multivalent ions screened by small monovalent counterions exhibit normal gas-liquid transitions of direct relevance to phase separation in charge-stabilized colloids. Conversely, extrapolation suggests the absence of such transitions for sufficiently small multivalent ions with large monovalent counterions.