Emerging exotic compositional order on approaching low-temperature equilibrium glasses

The ultimate fate of a glass former upon cooling has been a fundamental problem in condensed matter physics and materials science since Kauzmann. Recently, this problem has been challenged by a model with an extraordinary glass-forming ability effectively free from crystallisation and phase separation, two well-known fates of most glass formers, combined with a particle-size swap method. Thus, this system is expected to approach the ideal glass state if it exists. However, we discover exotic compositional order as the coexistence of space-spanning network-like structures formed by small-large particle connections and patches formed by medium-size particles at low temperatures. Therefore, the glass transition is accompanied unexpectedly by exotic compositional ordering inaccessible through ordinary structural or thermodynamic characterisations. Such exotic compositional ordering is found to have an unusual impact on structural relaxation dynamics. Our study thus raises fundamental questions concerning the role of unconventional structural ordering in understanding glass transition. Understanding glass transition would rely on the knowledge of the structural ordering upon slow cooling in the absence of crystallization or phase separation. The authors identify exotic compositional order, not accompanied by any thermodynamic signature, directly impacts the structural relaxation dynamics.