Employing Eq. 2, we fit the torsional angle dependent electronic couplings for the 153 monomer pairs and find that the median RMSE of fitting of electronic couplings for the monomer pair set is 0.03 eV; although, the magnitude of median RMSE is higher than that for the torsional potential fitting, median 𝜏 𝑘 (0) is ~2 orders of magnitude larger compared to median RMSE. In Fig. , we show the fitting for a sample monomer pair while the distribution of RMSE of fitting is given in the SI (see Fig. ). The simple relation between 𝜏 𝑘 and 𝜃 𝑘 , shown in Eq. 2, does not hold when the monomer fragment has negligible coupling with the neighbor moiety due to symmetry reason (e.g., pyridine moiety, with connecting sites at (2,5) positions, has HOMO of 𝜎-symmetry instead of 𝜋-symmetry; 46 see SI Fig. ), or because of the presence of nodal plane at the connecting carbon atoms (e.g., HOMO of 1,3-difluorobenzene with connecting sites at (2,5) positions; shown in SI Fig. ). In these cases, the assumption that the valence band is primarily dominated by the HOMOs of the monomer fragments does not hold. While generalization of the model with multiple frontier molecular orbitals is possible, in this work we prefer to keep the reduced model as simple as possible to allow comparison. In addition, we find 8 monomer pairs where the HOMO-HOMO couplings are less sensitive to torsional deformations (shown in SI Fig. ) and such effect has been identified earlier for monomer pairs with five-membered rings and pronounced single bond-double bond character within the ring. For these monomer pairs, fitting of the HOMO-HOMO coupling profile within a sinusoidal function proves unsatisfactory, yet the fitting can be improved by considering a larger cosine Fourier expansion (shown in SI Fig. ).