Figure shows that obtaining the derivatives from either displacement through dipole Figure : Equivalence of the dipole derivative dµ/dR and the force derivative dF/dξ for a range of elementary electrode reactions. Mean absolute error between dF/dξ and dµ/dR is 0.002 e (Equation ) or through forces (Equation ) is equivalent. Thus, the application of Method 2 is more appealing as it only relies on the atom centered forces from a DFT-calculation at a chosen structure (as in dF/dξ) instead of atomic displacements (as in dµ/dR). Note that this equivalence is only seen when the forces are properly converged; tests for different convergence criteria are shown in SI Note 1. Note that this method, combined with the extrapolation procedure in Equation , provides a direct way to determine potential dependent electrochemical barriers by using just the outputs of a DFT calculation along with the transition state structures, without the need for any a priori assumptions to its value.