As the distance from the CoM of the substrate to solvent molecules increases, the number of HBs for each solvent converges to the average bulk value, with two HBs for water molecules and one for methanol. Fig. displays a peak in the number of HB in the water close to the substrate, demonstrating the higher number of HBs in the first solvation shell for the RS (2.13), intermediate (2.43), and PS (2.49) compared to bulk water. Such an increase suggests the organisation of water molecules around the substrate during the reaction. In contrast, no such peak is observed in methanol, indicating that the solvent HB network is not influenced by the presence of substrate. The organisation of solvent molecules should lead to a reduction in free energy, as previously stated. Magsumov et al. demonstrated a linear relationship between the free energy of cavity formation and the volume of the cavity for various solvents through MD simulations utilising classical force fields. Applying their parameters for water and methanol, the change in cavity contribution from RS to post-TS was approximately -2.6 kcal mol -1 for the endo reaction in water, compared to around -1.1 kcal mol -1 in methanol, further evidencing that the reactions benefit more from the hydrophobic effect in the water than in methanol. These observations thus further support the role of the hydrophobic effect in the acceleration of DA reaction in water.