The properties of liquid Si-Ge binary systems at melting conditions deviate from those expected by the ideal alloy approximation. Particularly, a non-linear dependence of the dielectric functions occurs with the reflectivity of liquid Si-Ge reaching a maximum at 50\% Ge content, being 10\% higher than in pure Si or Ge. Using \textit{ab initio} methodologies, we modelled liquefied Si-Ge alloys, unveiling very high coordination numbers and poor symmetry in the first coordination shell with respect to Si and Ge, related to different bonding properties. We simulated optical functions, quantitatively replicating the aforementioned reflectivity trend and we highlighted a direct relationship between atomic structure and optical properties, indicating that the unusual optics arises from Si-Ge higher local coordination characterized by low symmetry. We forecast further implications for the overall class of these alloys. These findings expand our comprehension of liquefied semiconductors and are essential for implementing controlled laser melting procedures to highly dope these materials for advanced transistors, superconductors, sensors and plasmonic devices.
