The first microstructural analysis is the inter-fragments torsion distribution, i.e., one of the most significant parameter on electronic properties of SCPs, as obtained from "melt" and "soup" samples. Figure (left panel) shows a comparison between the inter-repeat unit torsion distributions obtained from "melt" (filled bars) and "soup" (unfilled bars) samples, as well as the Boltzmann distribution (dashed line) calculated based on the input torsional potential (obtained from DFT scans on the repeat-unit representative molecule). As clearly shown in Figure (left), the "soup" method can accurately capture the inter-monomer torsion distribution for all polymers. Figure in the SI illustrates that a similar conclusion is valid for the other torsional potentials. Moreover, the deviation of torsion angle distributions obtained from MD simulations from the Boltzmann distribution quantifies the impact of surrounding molecules and sidechains and the importance of using QC/MD schemes for calculating electronic structure properties instead of using ideal chain conformations for the QC calculations. It should be emphasised that the conformation of polymer chains in bulk are also influenced by (i) the mobility confinements imposed by the connectivity of the repeat units along the polymer chain, (ii) the conformation of sidechains attached to the backbone, and (iii) the steric effect of surrounding molecules (i.e., polymers in case of "melt" and repeat units in case of "soup" models)-thus, deviations in torsion angle distribution of MD models from the Boltzmann distribution is naturally expected. Also, such deviation is expected to be larger in case of smaller torsion barriers, e.g., compare the deviation in 2TT-2TT (~ 4 kBT) torsion in DPP-2TT polymer with T-DPP (~ 10 kBT) in DPP-DTT polymer in Figure .