Here, we present an efficient method for calculating adatom potential energy surfaces (PESs) and the activation barriers involved in the elementary steps of surface diffusion. Our method estimates a coupled potential energy profile based on the PESs of the decoupled processes and assumes bond order conservation. The associated barriers of migration were compared and validated against calculated barriers on common FCC(100) metal surfaces of Ag, Au, Cu, Pd, Pt, Rh, Ni, and Ir metals. The barrier prediction accuracy quantified by the mean absolute error (MAE) using the method is 0.12 eV, which is comparable to the accuracy of TS barriers by using Brønsted–Evans–Polanyi (BEP) relations. Given their high accuracy, the approximated activation barriers have the potential to predict the sintering and restructuring of metallic systems on-the-fly. Therefore, we believe that the model will help to improve and speed up the understanding of surface restructuring and sintering in heterogeneous catalysis.