From Chemical Drawing to Electronic Properties of Semiconducting Polymers in Bulk: A Tool for Chemical Discovery

A quantum chemistry (QC)/molecular dynamics (MD) scheme is developed to calculate electronic properties of semiconducting polymers in three steps: (i) constructing the polymer force field through a unified workflow, (ii) equilibrating polymer models, and (iii) calculating electronic structure properties (e.g., density of states and localization length) from the equilibrated models by QC approaches. Notably, as the second step of this scheme is generally the most time-consuming one, we introduce an alternative method to compute thermally averaged electronic properties in bulk, based on the simulation of a polymer chain in the solution of its repeat units, which is shown to reproduce the microstructure of polymer chains and their electrostatic effect (successfully tested for five benchmark polymers) 10 times faster than state-of-the-art methods. In fact, this scheme offers a consistent and speedy way of estimating electronic properties of polymers from their chemical drawings, thus ensuring the availability of a homogeneous set of simulations to derive structure–property relationships and material design principles. As an example, we show how the electrostatic effect of the polymer chain environment can disturb the localized electronic states at the band tails and how this effect is more significant in the case of diketopyrrolopyrrole polymers as compared to indacenodithiophene and dithiopheneindenofluorene ones.