The structure of poly(ethylene oxide) liquids: comparison of integral equation theory with molecular dynamics simulations and neutron scattering

Polymer reference interaction site model (PRISM) calculations and molecular dynamics (MD) simulations were carried out on poly(ethylene oxide) liquids using a force field of Smith, Jaffe, and Yoon. The intermolecular pair correlation functions and radius of gyration from theory were in very good agreement with MD simulations when the partial charges were turned off. When the charges were turned on, considerably more structure was seen in the intermolecular correlations obtained from MD simulation. Moreover, the radius of gyration increased by 38% due to electrostatic repulsions along the chain backbone. Because the partial charges greatly affect the structure, significant differences were seen between the PRISM calculations (without charges) and the wide angle neutron scattering measurements of Annis and coworkers for the total structure factor, and the hydrogen/hydrogen intermolecular correlation function. This is in contrast to previous PRISM calculations on poly (dimethyl siloxane).