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2016 ; 116
(13
): 7463-500
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Water: A Tale of Two Liquids
#MMPMID27380438
Gallo P
; Amann-Winkel K
; Angell CA
; Anisimov MA
; Caupin F
; Chakravarty C
; Lascaris E
; Loerting T
; Panagiotopoulos AZ
; Russo J
; Sellberg JA
; Stanley HE
; Tanaka H
; Vega C
; Xu L
; Pettersson LG
Chem Rev
2016[Jul]; 116
(13
): 7463-500
PMID27380438
show ga
Water is the most abundant liquid on earth and also the substance with the
largest number of anomalies in its properties. It is a prerequisite for life and
as such a most important subject of current research in chemical physics and
physical chemistry. In spite of its simplicity as a liquid, it has an enormously
rich phase diagram where different types of ices, amorphous phases, and anomalies
disclose a path that points to unique thermodynamics of its supercooled liquid
state that still hides many unraveled secrets. In this review we describe the
behavior of water in the regime from ambient conditions to the deeply supercooled
region. The review describes simulations and experiments on this anomalous
liquid. Several scenarios have been proposed to explain the anomalous properties
that become strongly enhanced in the supercooled region. Among those, the second
critical-point scenario has been investigated extensively, and at present most
experimental evidence point to this scenario. Starting from very low
temperatures, a coexistence line between a high-density amorphous phase and a
low-density amorphous phase would continue in a coexistence line between a
high-density and a low-density liquid phase terminating in a liquid-liquid
critical point, LLCP. On approaching this LLCP from the one-phase region, a
crossover in thermodynamics and dynamics can be found. This is discussed based on
a picture of a temperature-dependent balance between a high-density liquid and a
low-density liquid favored by, respectively, entropy and enthalpy, leading to a
consistent picture of the thermodynamics of bulk water. Ice nucleation is also
discussed, since this is what severely impedes experimental investigation of the
vicinity of the proposed LLCP. Experimental investigation of stretched water,
i.e., water at negative pressure, gives access to a different regime of the
complex water diagram. Different ways to inhibit crystallization through
confinement and aqueous solutions are discussed through results from experiments
and simulations using the most sophisticated and advanced techniques. These
findings represent tiles of a global picture that still needs to be completed.
Some of the possible experimental lines of research that are essential to
complete this picture are explored.
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