Ab initio study of chemical effect on structural properties of Ti–Al melts

We study chemical effect on the structural properties of Ti–Al melts, with the Al concentration systematically changed, via ab initio molecular dynamics simulations. By calculating the partial coordination numbers, we find a preferred connection between the nearest neighbors for Al–Ti pairs. This induces an excess Ti coordination in the cluster characterized by local five-fold symmetry in Voronoi tessellation. Structural entropy measured from the diversity of Voronoi polyhedrons shows an intriguing non-monotonic tendency with concentration: it first decreases to a minimum value at Ti₄₀Al₆₀, and then increases beyond this concentration. This implies a more ordered local structure induced by the chemical interaction at the intermediate compositions. The spatial correlation among the crystalline-like or the icosahedral-like clusters also exhibits the highest intensity for Al–Ti pairs, verifying the important role played by the chemical interaction in the local structure connectivity.