The polymer chain can be represented by a list of neighboring monomers along with the list of dihedral angles between them as mentioned in section I (see top and middle panel of Fig. ). We assume that the distributions of these dihedral angles in the polymer chain are uncorrelated and have the same distributions of dimers in gas phase; such an assumption can be considered as a reasonable starting point, but it can be systematically improved by performing MD simulations of the polymers to determine the actual dihedral angle distributions in presence of other chains. In addition, a generalized analytical function which can well-represent the electronic couplings (𝜏 𝑘 ) between localized orbitals on neighboring monomers (𝑘 and 𝑘 + 1) as a function of the corresponding dihedral angle (𝜃 𝑘 ) is required since distortions along the polymer backbone and subsequent disorder in the electronic couplings leads to localization of the charge-carriers. Analytical expressions of torsional potential and electronic coupling as a function of the dihedral angle are beneficial to represent the model with few parameters and could be used for implementing more advanced quantum dynamics methodologies like fewest switches surface hopping. We begin by considering the set of 36 polymers screened in Ref. as our primary set of polymers (the polymers are shown in supporting information (SI) Fig. ) to determine the analytical descriptors of the dimer torsional potentials and electronic couplings. These polymers correspond to hole-transport and ambipolar types and consist of 33 unique monomer units, with 7 having chemically inequivalent connection sites. We build a database of 153 monomer pairs, 83 corresponding to the monomer pairs within the above mentioned 36 polymers along with 70 related monomer pairs. The torsional potential profile of each of the monomer pairs is calculated within the density functional theory (DFT) at the B3LYP/6-311G+** level while the torsiondependent HOMO-HOMO coupling profile for the same is worked out within the localized molecular orbital method (LMOM), as detailed in Refs. and .