A final remark worth of discussion from Figure can be seen in the enthalpy-entropy breakdown for PIBSI, where there is a transition from an entropy penalty to an entropydriven adsorption for small distances (ξ ≲ 1.5 Å). This occurs because the surfactant, when expelling solvent molecules to approach the deposit, gains configurational freedom when binding onto the PAH aromatic groups, in comparison to when it is restricted to interact with adsorbed solvent. Furthermore, the enthalpic term becomes unfavourable at these small colvar values, which corresponds to the PIBSI head-group wrapping around the edge of the PAH molecule -see the adsorption energy of PIBSI-like head-groups at the PAH edge on Table . This would mean that, within this range of conformations, the enthalpic contribution of PIBSI (based on the force field interactions) with PAH is less preferred in comparison to the solvent adsorption.