Manifestations of the structural origin of supercooled water's anomalies in the heterogeneous relaxation on the potential energy landscape

Liquid water is well-known for its intriguing thermodynamic anomalies in the supercooled state. The phenomenological two-state models-based on the assumption of the existence of two types of competing local states (or, structures) in liquid water-have been extremely successful in describing water's thermodynamic anomalies. However, the precise structural features of these competing local states in liquid water still remain elusive. Here, we have employed a predefined structural order parameter-free approach to unambiguously identify two types of competing local states-entropically and energetically favored-with significantly different structural and energetic features in the TIP4P/2005 liquid water. This identification is based on the heterogeneous structural relaxation of the system in the potential energy landscape (PEL) during the steepest-descent energy minimization. This heterogeneous relaxation is characterized using order parameters inspired by the spin-glass transition in frustrated magnetic systems. We have further established a direct relationship between the population fluctuation of the two states and the anomalous behavior of the heat capacity in supercooled water. The composition-dependent spatial distribution of the entropically favored local states shows an interesting crossover from a spanning network-like single cluster to the spatially delocalized clusters in the close vicinity of the Widom line. Additionally, this study establishes a direct relationship between the topographic features of the PEL and the water's thermodynamic anomalies in the supercooled state and provides alternate markers (in addition to the locus of maxima of thermodynamic response functions) for the Widom line in the phase plane.