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Effect of chain architecture on the chain size, shape, and intrinsic viscosity was investigated by performing molecular dynamics simulations of polymer solutions in a good solvent. Four types of chains - linear, comb shaped, H-shaped, and star - were studied for this purpose using a model in which the solvent particles were considered explicitly. Results indicated that the chain length (N) dependence of the mean squared radius of gyration of the chains followed a power-law behavior (Rg²)1/2 ~ Nv with scaling exponents of u = 0.605, 0.642, 0.602, and 0.608, for the linear, comb shaped, H-shaped, and star shaped chains, respectively. The simulation results for the geometrical shrinking factor were higher than the prior theoretical predictions for comb shaped chains. Analysis of chain shape demonstrated that the star chains were significantly smaller and more spherical than the others, while the comb and H-shaped polymer chains showed a more cylindrical shape. It is shown that the intrinsic viscosity of the chains can be calculated by plotting the specific viscosity determined from simulations against the solution concentration. The intrinsic viscosity exhibited linear behavior with the reciprocal of the overlap concentration for all chain architectures studied. The molecular weight dependence of the intrinsic viscosity followed the Mark-Houwink relation, [n] = KMa, for all chain architectures. When comparing the calculated values of exponent a with the literature experimental values, agreement was found only for the H and star chains, and a disagreement for the linear and comb chains. The viscosity shrinking factor of the branched chains was compared with the available experimental data and the theoretical predictions and a general agreement was found. [ABSTRACT FROM AUTHOR]

We have studied the effect of chain topology on the structural properties and diffusion of polymers in a dilute solution in a good solvent. Specifically, we have used three different simulation techniques to compare the chain size and diffusion coefficient of linear and ring polymers in solution. The polymer chain is modeled using a bead-spring representation. The solvent is modeled using three different techniques: molecular dynamics (MD) simulations with a particulate solvent in which hydrodynamic interactions are accounted through the intermolecular interactions, multiparticle collision dynamics (MPCD) with a point particle solvent which has stochastic interactions with the polymer, and the lattice Boltzmann method in which the polymer chains are coupled to the lattice fluid through friction. Our results show that the three methods give quantitatively similar results for the effect of chain topology on the conformation and diffusion behavior of the polymer chain in a good solvent. The ratio of diffusivities of ring and linear polymers is observed to be close to that predicted by perturbation calculations based on the Kirkwood hydrodynamic theory. [ABSTRACT FROM AUTHOR]

Recent developments in techniques of micro- and nanofluidics have led to an increased interest in nanoscale hydrodynamics in confined geometries. In our previous study [S. C. Kohale and R. Khare, J. Chem. Phys. 129, 164706 (2008)], we analyzed the friction force experienced by a smooth spherical particle that is translating in a fluid confined between parallel plates. The magnitude of three effects—velocity slip at particle surface, the presence of confining surfaces, and the cooperative hydrodynamic interactions between periodic images of the moving particle—that determine the friction force was quantified in that work using molecular dynamics simulations. In this work, we have studied the motion of a rough spherical particle in a confined geometry. Specifically, the friction force experienced by a translating particle and the torque experienced by a rotating particle are studied using molecular dynamics simulations. Our results demonstrate that the surface roughness of the particle significantly reduces the slip at the particle surface, thus leading to higher values of the friction force and hence a better agreement with the continuum predictions. The particle size dependence of the friction force and the torque values is shown to be consistent with the expectations from the continuum theory. As was observed for the smooth sphere, the cooperative hydrodynamic interactions between the images of the sphere have a significant effect on the value of the friction force experienced by the translating sphere. On the other hand, the torque experienced by a spherical particle that is rotating at the channel center is insensitive to this effect. [ABSTRACT FROM AUTHOR]

We use molecular dynamics simulations to study the shear flow of a polymer solution in a nanochannel by using an explicit, atomistic model of the solvent. The length scales representing the chain size, channel size, and the molecular scale structure in these nanochannels are comparable. The diffusion and hydrodynamic interactions in the system are governed by the intermolecular interactions in the explicit solvent model that is used in the simulations. We study the cross stream migration of flexible polymer chains in a solution that is subjected to a planar Couette flow in a nanochannel. We present a detailed study of the effects of chain length, channel size, and solution concentration on the cross stream chain migration process. Our results show that when a dilute solution containing a longer and a shorter chain is subjected to shear flow, the longer chains that are stretched by the flow migrate away from the channel walls, while the shorter chains that do not stretch also do not exhibit this migration behavior. The thickness of the chain depletion layer at the channel surface resulting from cross stream migration is found to increase with an increase in the channel height. On the other hand, this degree of migration away from the channel walls is found to decrease with an increase in the solution concentration. In solutions with concentrations comparable to or greater than the overlap concentration, the depletion layer thickness in shear flow is found to be comparable or slightly smaller than that observed in the absence of flow. [ABSTRACT FROM AUTHOR]

We use molecular dynamics simulations to investigate the cooperative hydrodynamic interactions involved in the collective translation of a periodic array of spheres in a fluid which is confined between two atomistic surfaces. In particular, we study a spherical particle that is moving with a constant velocity parallel to the two confining surfaces. This central sphere along with its periodic images forms the translating two dimensional periodic grid. The cooperative hydrodynamic effects between neighboring spheres in the grid are determined by monitoring the friction force experienced by the spheres that are moving through an atomistic solvent. The dependence of the hydrodynamic cooperativity on the grid spacing is quantified by running simulations in systems with different sizes of the periodic box. Our results show a clear evidence of hydrodynamic cooperation between the spherical particles for grid spacing of 90σ and larger, where σ is the solvent molecular diameter. These cooperative interactions lead to a reduced value of the friction force experienced by these spheres as opposed to the case for a single sphere moving in an infinite quiescent fluid. The simulated friction force values are compared with the recent continuum mechanics predictions [Bhattacharya, J. Chem. Phys. 128, 074709 (2008)] for the same problem of the motion of a periodic grid of particles through a confined fluid. The simulated values of friction force were found to follow the same qualitative trend as the continuum results but the continuum predictions were consistently larger than the simulation results by approximately 22%. We attribute this difference to the fluid slip at the surface of the spherical particle, as measured in the simulations. [ABSTRACT FROM AUTHOR]

A new set of united-atom force field parameters is proposed for simulating the phase equilibria of branched alkanes. These parameters complement the already existing set of Nath, Escobedo, and de Pablo revised (NERD) [Nath et al., J. Chem. Phys. 105, 4391 (1998); Nath and de Pablo, Mol. Phys. 98, 231 (2000)] force field parameters. The proposed force field is used to study vapor–liquid equilibria for various isomers of alkanes up to C[sub 8]. Results of simulations are found to be in good agreement with available experimental data. © 2001 American Institute of Physics. [ABSTRACT FROM AUTHOR]

The details of the molecular model, including the procedure used for developing the force field parameters for alcohol alcohol s are presented. These details are discussed with the results from the Gibbs ensemble simulation procedures.

Investigates the rheological, thermodynamic and structural behavior of linear and branched alkanes in simple shear using nonequilibrium-dynamics simulation of united atom model fluids. Results for the zero-shear viscosity of linear alkanes; Simulation results for intermediate molecular weight linear alkanes.

Investigates the behavior of simple fluids under shear using molecular dynamics simulations. Background on the simulated system consisting of a fluid confined between atomistic walls moved in opposite directions; Comparison of approaches for shear flow simulations.