The detailed atomistic modeling of electrochemically deposited metal monolayers is challenging due to the complex structure of the metal-solution interface and the critical effects of surface elec- trification during electrode polarization. Accurate models of interfacial electrochemical equilibria are further challenged by the need to include entropic effects to obtain accurate surface chemical potentials. We present an embedded quantum-continuum model of the interfacial environment that addresses each of these challenges and study the underpotential deposition of silver on the gold (100) surface. We leverage these results to parameterize a cluster expansion of the electrified in- terface and show through grand canonical Monte Carlo calculations the crucial need to account for variations in the interfacial dipole when modeling electrodeposited metals under finite-temperature electrochemical conditions.