CC BY-NC-ND 3.0 UnportedSelli, DanieleBaburin, Igor A.Martoňák, RomanLeoni, Stefano2025-03-042025-03-042013https://oa.tib.eu/renate/handle/123456789/18748https://doi.org/10.34657/17767Group-IVa elements silicon and germanium are known for their semiconducting properties at room temperature, which are technologically critical. Metallicity and superconductivity are found at higher pressures only, Ge β-tin (tI4) being the first high-pressure metallic phase in the phase diagram. However, recent experiments suggest that metallicity in germanium is compatible with room conditions, calling for a rethinking of our understanding of its phase diagram. Missing structures can efficiently be identified based on structure prediction methods. By means of ab initio metadynamics runs we explored the lower-pressure region of the phase diagram of germanium. A monoclinic germanium phase (mC16) with four-membered rings, less dense than diamond and compressible into β-tin phase (tI4) was found. Tetragonal bct-5 appeared between diamond and tI4. mC16 is a narrow-gap semiconductor, while bct-5 is metallic and potentially still superconducting in the very low pressure range. This finding may help resolving outstanding experimental issues.enghttps://creativecommons.org/licenses/by-nc-nd/3.0/500600Computer SimulationDiamondElectric ConductivityGermaniumMetalsModels, ChemicalModels, MolecularPressureSemiconductorsSiliconTemperatureThermodynamicsTindiamondgermaniummetalsilicontinarticlechemical modelchemical structurechemistrycomputer simulationelectric conductivitypressuresemiconductortemperaturethermodynamicsArticle