where the angle brackets denote ensemble averages. The mean value for the force in each bin coming from these samples is used to compute the gradient as in Equation and, through numerical integration, the free energy value G. The PMF is eventually shifted by substracting the Jacobian term, so that the free energy value at large distances is zeroed where the deposit-DCA binding interactions fade away. However, it is important to note that albeit the sampling is facilitated along ξ using the ABF approach, its convergence still depends on the relaxation of the other (orthogonal) degrees of freedom. For studying adsorption processes, this would imply the many different configurations along the planes parallel (e.g.