Search results for "Statistical"
showing 10 items of 4960 documents
Atomistic Molecular Dynamics Simulations of the Static and Dynamic Properties of a Polyethylene Melt
1999
I will discuss in this work the atomistic modelling of polymer melts using Molecular Dynamics (MD) simulations. After a general introduction into the problems one faces in the computer simulation of polymers in general and the atomistic simulations in particular, I will present some recent work on the atomistic modelling of an — C 100 H 202 melt,i.e. short chain polyethylene (PE). The aim of this work is to establish a quantitatively validated atomistic model which then can be used in two directions. One direction is the generation of input for the calibration of parameters in coarse-grained models, which in turn can be used to simulate the polymer under investigation over a much broader te…
Entropy theory and glass transition: A test by Monte Carlo simulation
1997
This article reviews the results of a test of the Gibbs-DiMarzio theory by Monte Carlo Simulation. The simulation employed the bond-fluctuation model on a simple cubic lattice. This model incorporates two kinds of interactions: the excluded volume interaction among all monomers of the melt and an internal energy of the chains, which favors large bonds and makes the chains stiffen with decreasing temperature. The stiffening of the chains leads to an increase of their volume requirements, which competes with the packing constraints at low temperatures. This competition strongly slows down the structural relaxation of the melt and induces the glassy behavior. The model therefore takes into acc…
Polymer translocation through a nanopore induced by adsorption: Monte Carlo simulation of a coarse-grained model
2004
Dynamic Monte Carlo simulation of a bead-spring model of flexible macromolecules threading through a very narrow pore in a very thin rigid membrane are presented, assuming at the cis side of the membrane a purely repulsive monomer-wall interaction, while the trans side is attractive. Two choices of monomer-wall attraction epsilon are considered, one choice is slightly below and the other slightly above the "mushroom to pancake" adsorption threshold epsilon(c) for an infinitely long chain. Studying chain lengths N=32, 64, 128, and 256 and varying the number of monomers N(trans) (time t=0) that have already passed the pore when the simulation started, over a wide range, we find for epsiloneps…
Classification of Complex Molecules
2009
Algorithms for classification and taxonomy based on criteria, e.g., information entropy and its production are proposed. In molecular classification, the feasibility of replacing a given molecule (e.g, anaesthetic) by similar ones in the composition of a complex drug is studied. Some local anaesthetics currently in use are classified using characteristic chemical properties of different portions of their molecules. In taxonomy, the detailed comparison of the sequences (primary structures) of biomolecules, proteins or nucleic acids, allows the reconstruction of a molecular phylogenetic tree for some species, e.g. the 1918 influenza virus. The method is applied to the classifications of: (1) …
Theory and Simulation of Multiphase Polymer Systems
2010
The theory of multiphase polymer systems has a venerable tradition. The 'classical' theory of polymer demixing, the Flory-Huggins theory, was developed already in the forties of the last century. It is still the starting point for most current approaches -- be they improved theories for polymer (im)miscibility that take into account the microscopic structure of blends more accurately, or sophisticated field theories that allow to study inhomogeneous multicomponent systems of polymers with arbitrary architectures in arbitrary geometries. In contrast, simulations of multiphase polymer systems are relatively young. They are still limited by the fact that one must simulate a large number of lar…
Dynamical heterogeneities in glass-forming materials
1996
ABSTRACTCooperative dynamics around the glass transition leads to complex motional behavior of the individual molecules, resulting in non-exponential relaxation. The nature of this non-exponentiality is clarified theoretically as well as experimentally. The non-exponentiality may be due to heterogeneous relaxation (superposition of exponential processes with different rate constants) or homogeneous relaxation (identical intrinsically non-exponential processes). A precise definition of both limits is given. It is shown that the type of relaxation, i.e. to which degree heterogeneous and homogeneous contributions are present, reflects geometrical properties of the dynamics. The heterogeneous c…
Monte Carlo methods for polymer chains in two - dimensional geometries (polymers at surfaces and interfaces)
1993
Coarse-grained models of polymers at interfaces can be defined such that their treatment by Monte Carlo simulation is most convenient and efficient for the problem at hand. This simulation strategy is briefly illustrated with three examples: (1) The orientational ordering of rigid rod-like polymers grafted to a surface, where “table methods” can be used, applying a fine discretization of the angles describing rod orientation. (2) Surface enrichment of one species in a polymer blend is treated by a semi-grand-canonical technique. (3) The number of configurations and structure of a star polymer attached with its center to a wall is studied by a “growth technique” generalizing simple sampling …
Semidilute and Concentrated Polymer Solutions near Attractive Walls: Dynamic Monte Carlo Simulation of Density and Pressure Profiles of a Coarse-Gra…
1997
Using a bead−spring model of flexible polymer chains, we study polymer adsorption from solutions onto attractive planar walls, varying both the strength of the adsorption potential e and the concentration of the solution over a wide range. Treating the case of good solvents, the profiles of density and pressure are computed and it is shown that thermal equilibrium between the adsorbed layer and the bulk solution is obtained. The case of a wall with purely repulsive potential under otherwise identical conditions is treated for comparison. It is shown that for the strongly adsorbing wall there is a pronounced layering, while a layered structure at the repulsive wall occurs only for high conce…
Nonlocal van der Waals Approach Merged with Double-Hybrid Density Functionals: Toward the Accurate Treatment of Noncovalent Interactions
2015
Noncovalent interactions drive the self-assembly of weakly interacting molecular systems to form supramolecular aggregates, which play a major role in nanotechnology and biochemistry. In this work, we present a thorough assessment of the performance of different double-hybrid density functionals (PBE0-DH-NL, revPBE0-DH-NL, B2PLYP-NL, and TPSS0-DH-NL), as well as their parent hybrid and (meta)GGA functionals, in combination with the most modern version of the nonlocal (NL) van der Waals correction. It is shown that this nonlocal correction can be successfully coupled with double-hybrid density functionals thanks to the short-range attenuation parameter b, which has been optimized against ref…
The Nonlocal Correlation Density Functional VV10
2015
Abstract In this chapter, we review the most relevant attempts to merge the Vydrov and van Voorhis nonlocal density-dependent functional kernel (VV10) with modern density functionals to accurately describe van der Waals interactions with a reasonable computational cost. The chapter is organized by providing first an introduction of the relevance of van der Waals interactions and the difficulties of common density functionals to describe these forces. Second, the historical developments that eventually give rise to the most modern formulation of the nonlocal density functional VV10 are briefly addressed. Then, an overview of its technical formulation, adjustable parameters, and implementatio…