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