In our recent study, we combined the techniques of liquid micro-jets with synchrotron X-ray photoelectron (PE) spectroscopy to determine the binding energies and the densities of states of the excess electrons in liquid ammonia over a broad concentration range of 0.08-9.7 MPM. Figure displays the DoS determined from the G 0 W 0 calculations (refined using the Boltztrap2 code, see SI) based on 100 AIMD snapshots at intervals of 200 femtoseconds from 4 trajectories for each of the two systems at 3.0 MPM and 11.1 MPM, plotted against experimental data 5 for direct comparison. The experimental PE spectra reveal a clear picture of a gradual EMT. Employing a fitting procedure has enabled quantification of the decrease of the solvated (di)electron peak pertinent to the electrolyte with a simultaneous rise of the metallic spectral features, i.e, the signatures of the conduction band as well as features corresponding to plasmonic oscillations, as the alkali metal concentration increases. The calculated DoSs align with experimental spectra at comparable concentrations of 3.4 and 9.7 MPM. Namely, at the higher concentration where the system is metallic all the time, both simulation and experiment exhibit an asymmetric peak corresponding to the conduction band sharply ending at the Fermi level (the slight offset of about 0.2 eV between the calculation and measurement is within the accuracy of the absolute calibration of the experiment). At the lower concentration, the calculated DoS can be separated into contributions from electrolyte and metallic snapshots. While this is not possible for the experiment which averages the signal over time, the measured PE signal can still be split (after subtracting features corresponding to plasmonic oscillations) into direct contributions from localised dielectrons and delocalised metallic electrons. We see that the signal calculated for the electrolyte snapshots aligns well with the experimental contribution from the dielectrons. The comparison for the metallic snapshots is less straightforward since the corresponding densities of states result from a superposition of localised and delocalised electrons. The latter contribution nevertheless aligns well with the measured "metallic part" of the spectrum. This general agreement between calculations and experiments underscores the suitability of G 0 W 0 for capturing the essential physical phenomena associated with the EMT.