Ultrafast molecular dynamics approach to quantify structural and transport properties of ion exchange polymer: a case study on perfluorinated sulfonic acid polymer

Abstract

A computationally efficient molecular dynamics (MD) simulation approach for evaluating the transport and structural properties of ion exchange polymers (IEPs) is proposed. Prediction of transport and structural properties of IEPs using MD simulation is beneficial in understanding structure-property relations and to design advanced tailor-made variants of such polymers. The IEP is a complex network of polymer chains with ionic end groups. Hence, computational robustness plays a key role, especially in large simulation cells, in avoiding iterative and often time-consuming process to arrive at definitive solutions in terms of physical properties. A novel and robust approach is presented in general and evaluated for perfluorosulfonic acid (PFSA) polymer structure as a case study. While prior researches have analysed transport and structural properties of such polymers using MD simulation in detail, there is a lack of information on the model standard and equilibration protocol. To this end, the present article compares the proposed algorithm to conventional approaches for structure equilibration and demonstrate that the variation in diffusion coefficients (water and hydronium ions) reduces as the number of chains increases, with significantly reduced errors observed in 14 and 16 chains models, even at elevated hydration. The proposed method to achieve equilibration is ?200% more efficient than conventional annealing and ?600% more efficient than the lean method. © 2025 The Royal Society of Chemistry.