Inspection of the TS indicates that applying a positive FZ polarizes the TS structure and hence enhances its asynchronicity. In the aqueous phase, as Fz increases from 0 to 0.1 V/Å, μZ of the TS increases from 3.03 D to 4.02 D, because a larger electron density fraction is transferred from the CPD-moiety to the ALT-moiety, where the Mulliken charge of the latter changes from -0.25 e to -0.29 e (Figure ). At the same time, the C1-C4 bond distance (denoted as CV1) increases and the C2-C3 bond distance (denoted as CV2) decreases. Their difference, ΔCV = CV1-CV2, is defined as the asynchronicity of the TS. As a result, ΔCV increases from 0.30 Å under field-free condition to 0.33 Å under Fz = 0.1 V/Å. These observations are in line with the work of Bickelhaupt and Shaik groups. When FZ=0.1 V/Å, the above calculation leads to a barrier drop of 2.2 kcal/mol compared to the field-free condition in the aqueous phase modeled with implicit solvation. To account for the solute-solvent interaction, we further performed AIMD simulations in combination with welltempered MetD with explicit solvent molecules under a 0.1 V/Å static EEF. Simulation details are present in the Supporting Information. After the application of the EEF, there is a noticeable change in the overall orientation of the water molecules. This can be clearly observed from the snapshots reported in Figure where, compared to the field-free condition, the orientation of water molecules becomes more ordered under the field action. During the simulation, the angle between the EEF and the reactants dipole moment is maintained in a range between 20° and 80° (Figure ), an arrangement facilitating the charge transfer from CPD to ALT.