The computational framework to obtain the free energies of formation consist of three parts. First, we performed DFT-MD simulations to obtain the trajectories of the atomic structures and the internal energies of the interfaces. Second, we calculated the entropy of each system using the 2PT method. Finally, we evaluated the free energy changes with respect to three different experimentally relevant reference systems corresponding to either metal-water surface tension, surface solvation energy, or work of adhesion measurements, as shown in Figure . In practice, the reference systems are bulk forms of both metal and water, the metallic surface and bulk for water, or the metal and water surfaces, respectively. FIG. . Thermodynamic cycle used to assess the formation of solid-liquid interfaces and to illustrate the connections between different systems, references, and measurable quantities. The black arrows correspond to the route used in the present work and the equations defined in the SI. The grey arrows present an alternative route to connect the surface and bulk references. The red arrows show the DFT models of the sl, sv, and lv interfaces as well as their connections with the experimentally relevant systems. The highlighted (purple frame) system depicts the ideal experimental sl interface, which is our target of evaluation. The top right system corresponds to the DFT model of the sl interface used in the actual simulations. The bottom systems display the alternative reference schemes to obtain γ sl , F solv , or W ad . The rightmost panel shows the auxiliary systems needed for closing the thermodynamic cycle. The different interfaces present in each system are colored as sl: purple, sv: grey, and lv: cyan.