Strategies for the Development of Conjugated Polymer Molecular Dynamics Force Fields Validated with Neutron and X-ray Scattering.

Conjugated polymers (CPs) enable a wide range of lightweight, lower cost, and flexible organic electronic devices, but a thorough understanding of relationships between molecular structure and dynamics and electronic performance is critical for improved device efficiencies and for new technologies. Molecular dynamics (MD) simulations offer in silico insight into this relationship, but their accuracy relies on the approach used to develop the model's parameters or force field (FF). In this Perspective, we first review current FFs for CPs and find that most of the models implement an arduous reparameterization of inter-ring torsion potentials and partial charges of classical FFs. However, there are few FFs outside of simple CP molecules, e.g., polythiophenes, that have been developed over the last two decades. There is also limited reparameterization of other parameters, such as nonbonded Lennard-Jones interactions, which we find to be directly influenced by conjugation in these materials. We further provide a discussion on experimental validation of MD FFs, with emphasis on neutron and X-ray scattering. We define multiple ways in which various scattering methods can be directly compared to results of MD simulations, providing a powerful experimental validation metric of local structure and dynamics at relevant length and time scales to charge transport mechanisms in CPs. Finally, we offer a perspective on the use of neutron scattering with machine learning to enable high-throughput parametrization of accurate and experimentally validated CP FFs enabled not only by the ongoing advancements in computational chemistry, data science, and high-performance computing but also using oligomers as proxies for longer polymer chains during FF development.

Assessment of molecular dynamics simulations for amorphous poly(3-hexylthiophene) using neutron and X-ray scattering experiments.

The molecular morphology and dynamics of conjugated polymers in the bulk solid state play a significant role in determining macroscopic charge transport properties. To understand this relationship, molecular dynamics (MD) simulations and quantum mechanical calculations are used to evaluate local electronic properties. In this work, we investigate the importance of system and simulation parameters, such as force fields and equilibration methods, when simulating amorphous poly(3-hexylthiophene) (P3HT), a model semiconducting polymer. An assessment of MD simulations for five different published P3HT force fields is made by comparing results to experimental wide-angle X-ray scattering (WAXS) and to a broad range of quasi-elastic neutron scattering (QENS) data. Moreover, an in silico analysis of force field parameters reveals that atomic partial charges and torsion potentials along the backbone and side chains have the greatest impact on structure and dynamics related to charge transport mechanisms in P3HT.