Mapping atomistic to coarse-grained polymer models using automatic simplex optimization to fit structural properties

We develop coarse-grained force fields for poly (vinyl alcohol) and poly (acrylic acid) oligomers. In both cases, one monomer is mapped onto a coarse-grained bead. The new force fields are designed to match structural properties such as radial distribution functions of various kinds derived by atomistic simulations of these polymers. The mapping is therefore constructed in a way to take into account as much atomistic information as possible. On the technical side, our approach consists of a simplex algorithm which is used to optimize automatically non-bonded parameters as well as bonded parameters. Besides their similar conformation (only the functional side group differs), poly (acrylic acid) was chosen to be in aqueous solution in contrast to a poly (vinyl alcohol) melt. For poly (vinyl alcohol) a non-optimized bond angle potential turns out to be sufficient in connection with a special, optimized non-bonded potential. No torsional potential has to be applied here. For poly (acrylic acid), we show that each peak of the radial distribution function is usually dominated by some specific model parameter(s). Optimization of the bond angle parameters is essential. The coarse-grained forcefield reproduces the radius of gyration of the atomistic model. As a first application, we use the force field to simulate longer chains and compare the hydrodynamic radius with experimental data.Comment: 34 pages, 3 tables, 16 figure

Local chain ordering in amorphous polymer melts: Influence of chain stiffness

Molecular dynamics simulation of a generic polymer model is applied to study melts of polymers with different types of intrinsic stiffness. Important static observables of the single chain such as gyration radius or persistence length are determined. Additionally we investigate the overall static melt structure including pair correlation function, structure function and orientational correlation function.Comment: 13 pages, 15 figures, PCCP accepte

Local Reorientation Dynamics of Semiflexible Polymers in the Melt

The reorientation dynamics of local tangent vectors of chains in isotropic amorphous melts containing semiflexible model polymers was studied by molecular dynamics simulations. The reorientation is strongly influenced both by the local chain stiffness and by the overall chain length. It takes place by two different subsequent processes: A short-time non-exponential decay and a long-time exponential reorientation arising from the relaxation of medium-size chain segments. Both processes depend on stiffness and chain length. The strong influence of the chain length on the chain dynamics is in marked contrast to its negligible effect on the static structure of the melt. The local structure shows only a small dependence on the stiffness, and is independent of chain length. Calculated correlation functions related to double-quantum NMR experiments are in qualitative agreement with experiments on entangled melts. A plateau is observed in the dependence of segment reorientation on the mean-squared displacement of the corresponding chain segments. This plateau confirms, on one hand, the existence of reptation dynamics. On the other hand, it shows how the reptation picture has to be adapted if, instead of fully flexible chains, semirigid chains are considered.Comment: 29 pages, several figures, accepted by Macromolecule

Orientation Correlation in Simplified Models of Polymer Melts

We investigate mutual local chain order in systems of fully flexible polymer melts in a simple generic bead-spring model. The excluded-volume interaction together with the connectivity leads to local ordering effects which are independent of chain length between 25 and 700 monomers, i.e. in the Rouse as well as in the reptation regime. These ordering phenomena extend to a distance of about 3 to 4 monomer sizes and decay to zero afterwards.Comment: 5 pages, 3 figure

Mapping atomistic to coarse-grained polymer models using automatic simplex optimization to fit structural properties

We develop coarse-grained force fields for poly (vinyl alcohol) and poly (acrylic acid) oligomers. In both cases, one monomer is mapped onto a coarse-grained bead. The new force fields are designed to match structural properties such as radial distribution functions of various kinds derived by atomistic simulations of these polymers. The mapping is therefore constructed in a way to take into account as much atomistic information as possible. On the technical side, our approach consists of a simplex algorithm which is used to optimize automatically non-bonded parameters as well as bonded parameters. Besides their similar conformation (only the functional side group differs), poly (acrylic acid) was chosen to be in aqueous solution in contrast to a poly (vinyl alcohol) melt. For poly (vinyl alcohol) a non-optimized bond angle potential turns out to be sufficient in connection with a special, optimized non-bonded potential. No torsional potential has to be applied here. For poly (acrylic acid), we show that each peak of the radial distribution function is usually dominated by some specific model parameter(s). Optimization of the bond angle parameters is essential. The coarse-grained forcefield reproduces the radius of gyration of the atomistic model. As a first application, we use the force field to simulate longer chains and compare the hydrodynamic radius with experimental data.Comment: 34 pages, 3 tables, 16 figure

Local Structure and Dynamics of Trans-polyisoprene oligomers

Mono- and poly-disperse melts of oligomers (average length 10 monomers) of trans-1,4-polyisoprene are simulated in full atomistic detail. The force-field is developed by means of a mixture of ab initio quantum-chemistry and an automatic generation of empirical parameters. Comparisons to NMR and scattering experiments validate the model. The local reorientation dynamics shows that for C$-$H vectors there is a two-stage process consisting of an initial decay and a late-stage decorrelation originating from overall reorientation. The atomistic model can be successfully mapped onto a simple model including only beads for the monomers with bond springs and bond angle potentials. End-bridging Monte Carlo as an equilibration stage and molecular dynamics as the subsequent simulation method together prove to be a useful method for polymer simulations.Comment: 25 pages, 15 figures, accepted by Macromolecule