Polymer force fields from ab initio studies of small model molecules: Can we achieve chemical accuracy?

We endeavor to demonstrate, using poly(ethylene oxide) (PEG) as a model system, that atomistic force fields based upon high-level quantum chemistry calculations on small model molecules can accurately reproduce static and dynamic properties of polymer melts and solutions. The validity of the force field is demonstrated through (1) comparison of predicted properties of the small molecules obtained from quantum chemistry with experiment, (2) comparison of properties predicted by the force field for larger molecules with those determined from quantum chemistry and (3) comparison of static and dynamic properties obtained from molecular dynamics simulations of PEO melts and PEO/LiI solutions using the quantum chemistry based force field with experimental neutron scattering and NMR measurements on these systems. (C) 1997 Published by Elsevier Science B.V.