where F(T ) is the canonical free energy at temperature T , and ⟨E(T )⟩ and ⟨S(T )⟩ denote the expectation values of the internal energy and the total entropy, respectively, of the systems. The expectation values were obtained as time averages over the DFT-MD trajectories. The total entropies were evaluated within the 2PT method from the DFT-MD trajectories using the DoSPT code by Caro et al. In brief, the 2PT method computes the entropy in three steps: 1) splitting the DFT-MD trajectory dynamics into vibrational, rotational, and translational degrees of freedom (DoF), 2) computing the DoS functions for each DoF from the velocity auto-correlation functions, and 3) computing the total entropy as a sum of the three modes obtained using a weighted integral over the DoS of the corresponding DoF. While originally developed for liquids , the 2PT formalism can also be applied to solidliquid systems without issues. Here we customized the use of the DoSPT code from tetragonal to monoclinic simulation cells. In the interfacial systems, the entropy can further be divided into metal and water contributions by defining the so called supergroups in the DoSPT program. To decompose even further, we partitioned the entropy of water into interface and bulk-like regions according to the distance of the molecules from the metal surface.