Dynamical rigidity transition in the viscoelastic properties of chalcogenide glass-forming liquids

Abstract The viscoelastic properties of supercooled AsxSe100-x (0 ≤ x ≤ 30) and AsxSe100-x-yIy (x = 20, 30 and y = 10, 20) liquids are studied using oscillatory parallel plate rheometry. In addition to the α-relaxation process, the shear relaxation of liquids with selenium chains longer than ~ 3 atoms is also characterized by a low-frequency polymeric mode. The temporal decoupling of this low-frequency soft/floppy relaxation mode from that of the α-relaxation mode is a unique function of the average selenium chain length. The floppy mode abruptly vanishes for liquids with average chain lengths shorter than ~ 3 Se atoms, thus implying a dynamical rigidity transition. When taken together, these results indicate that, contrary to the conventional wisdom, the pertinent structural variable associated with such transition in the viscoelastic behavior is not the average coordination number but instead the intermediate-range structural elements such as the average selenium chain length.