Table : Binding energies (∆E(z min )) in kcal/mol and equilibrium distances (z min ) in Å for various π-systems, including benzene, thiophene, benzenethiol, "Free TBT monomer", and "PTBT constituent monomer". These values were obtained using different computational approaches: B3LYP/6-311++G(d,p), OPLS-AA, and OPLS-AA with corrections (OPLS-AA/corr.). For the "Free TBT monomer" and "PTBT constituent monomer", the energy profiles are divided into three distinct zones: Zone-1, Zone-2, and Zone-3 (see Fig. (a) and Fig. In Fig. , we present the binding energy surfaces from B3LYP/6-311++G(d,p) (a), OPLS-AA (b), and OPLS-AA/corr. (c). In (a), DFT calculations reveal a strong cation-π interaction, with binding energy peaking centrally due to the electron-rich π-system attracting the Li + ion. In contrast, the uncorrected OPLS-AA force field in (b) fails to capture this strong interaction, reflecting a weaker electrostatic effect. Furthermore, this discrepancy arises because the original OPLS-AA force field has not explicitly accounted for the cation-π interaction in the development of force field parameters. The corrected OPLS-AA/corr., which explicitly considered the cation-π interaction, result in (c) aligns more closely with the DFT findings, showing enhanced binding not only at the benzene center but also in the near-field region. This highlights the effectiveness of the correction methods used. However, the far-field region, with OPLS-AA/corr., is not well captured. This is because, during the fitting procedure, we did not include all points equidistantly across the entire spatial range of the molecule. Including all points would put too little weight on during fitting the global minimum and the surrounding region -which is crucial for cation-π interaction.