Abstract
Molecular dynamics (MD) simulations are reported for [polyethylene glycol (PEG)200], a polydisperse mixture of ethylene glycol oligomers with an average molar weight of 200 g·mol(-1). As a first step, available force fields for describing ethylene glycol oligomers were tested on how accurately they reproduced experimental properties. They were found to all fall short on either reproducing density, a static property, or the self-diffusion coefficient, a dynamic property. Discrepancies with the experimental data increased with the increasing size of the tested ethylene glycol oligomer. From the available force fields, the optimized potential for liquid simulation (OPLS) force field was used to further investigate which adjustments to the force field would improve the agreement of simulated physical properties with experimental ones. Two parameters were identified and adjusted, the (HO)-C-C-O proper dihedral potential and the polarity of the hydroxy group. The parameter adjustments depended on the size of the ethylene glycol oligomer. Next, PEG200 was simulated with the OPLS force field with and without modifications to inspect their effects on the simulation results. The modifications to the OPLS force field significantly decreased hydrogen bonding overall and increased the propensity of intramolecular hydrogen bond formation at the cost of intermolecular hydrogen bond formation. Moreover, some of the tri- and more so tetraethylene glycol formed intramolecular hydrogen bonds between the hydroxy end groups while still maintaining strong intramolecular interactions with the ether oxygen atoms. These observations allowed the interpretation of the obtained RDFs as well as structural properties such as the average end-to-end distances and the average radii of gyration. The MD simulations with and without the modifications showed no evidence of preferential association of like-oligomers to form clusters nor any evidence of long-range ordering such as a side-by-side stacking of ethylene glycol oligomers. Instead, the simulation results support the picture of PEG200 being a random mixture of its ethylene glycol oligomer components. Finally, additional MD simulations of a binary mixture of tri-and hexaethylene glycol with the same average molar weight as PEG200 revealed very similar structural and physical properties as for PEG200.