A scheme to compute laterally resolved free energy surfaces and spectral signatures of specifically adsorbed ions on electrode surfaces from their ab initio molecular dynamics (AIMD) trajectories is proposed. Considering H-covered Pt(111) electrodes, both in contact with water and vacuum and for various H coverages, we systematically explore the impact of explicit water and H-coverage on site occupancy, providing direct insight into the proportion of underpotential and overpotential deposited hydrogen adsorbates. Extending this approach further, we can obtain laterally resolved vibrational spectra of the Pt-H stretch modes. We discuss how the difference between the free energy basins of the on-top and fcc-hollow adsorption sites explains the features of the experimentally observed spectral fingerprints in this system. These fingerprints do not contain only information about the stable and metastable adsorption sites but also about intermediate short-lived adsorbate configurations. Our results also show that for these properties chemisorbed H2O acts as a spectator and does not qualitatively influence the relative stabilities of the adsorption sites and their spectral fingerprints.