The present review is related to the studies of structural changes observed in metallic glass-forming liquids on cooling and subsequent vitrification in terms of radial distribution function and its analogues. These structural changes are discussed in relationship with liquid’s properties, especially the relaxation time and viscosity. These changes are found to be directly responsible for liquid fragility: deviation of the temperature dependence of viscosity of a supercooled liquid from the Arrhenius equation through modification of the activation energy for viscous flow. Further studies of this phenomenon are necessary to provide direct mathematical correlation between the atomic structure and properties.

We utilise displacement analysis of Cu-atoms between the chemical bond-centred Voronoi polyhedrons to reveal structural changes at the glass transition. We confirm that the disordered congruent bond lattice of Cu loses its rigidity above the glass transition temperature (Tg) in line with Kantor–Webman theorem due to percolation via configurons (broken Cu-Cu chemical bonds). We reveal that the amorphous Cu has the Tg = 794 ± 10 K at the cooling rate q = 1 × 1013 K/s and that the determination of Tg based on analysis of first sharp diffraction minimum (FDSM) is sharper compared with classical Wendt–Abraham empirical criterion.