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 mode l system, that atomistic force fields based upon high-level quantum ch emistry calculations on small model molecules can accurately reproduce static and dynamic properties of polymer melts and solutions. The val idity of the force held is demonstrated through (1) comparison of pred icted properties of the small molecules obtained from quantum chemistr y with experiment, (2) comparison of properties predicted by the force field for larger molecules with those determined from quantum chemist ry and (3) comparison of static and dynamic properties obtained from m olecular dynamics simulations of PEO melts and PEO/LiI solutions using the quantum chemistry based force field with experimental neutron sca ttering and NMR measurements on these systems. (C) 1997 Published by E lsevier Science B.V.