Communication: Diffusion constant in supercooled water as the Widom line is crossed in no man’s land

Ni, Yicun; Hestand, Nicholas J.; Skinner, James

doi:10.1063/1.5029822

Cited by 17 publications

(13 citation statements)

References 60 publications

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“…In this respect, further study is currently undertaken toward the appropriate inference of the self-diffusion constant D, particularly at much deeper supercooled states inside the so-called no man's land region. 49,50,[59][60][61] . It is also worthy to apply our cage-jump model to various water models to give deeper insight into the role of the H-bond breakage on the molecular diffusivity in supercooled water.…”

Section: Discussionmentioning

confidence: 99%

Diffusion dynamics of supercooled water modeled with the cage-jump motion and hydrogen-bond rearrangement

Kikutsuji

Kim

Matubayasi

2019

The Journal of Chemical Physics

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The slow dynamics of glass-forming liquids is generally ascribed to the cage-jump motion. In the cage-jump picture, a molecule remains in a cage formed by neighboring molecules, and after a sufficiently long time, it jumps to escape from the original position by cage-breaking. The clarification of the cage-jump motion is therefore linked to unraveling the fundamental element of the slow dynamics. Here, we develop a cagejump model for the dynamics of supercooled water. The caged and jumping states of a water molecule are introduced with respect to the hydrogen-bond (H-bond) rearrangement process, and describe the motion in supercooled states. It is then demonstrated from the molecular dynamics simulation of the TIP4P/2005 model that the characteristic length and time scales of cage-jump motions provide a good description of the selfdiffusion constant that is determined in turn from the long-time behavior of the mean square displacement. Our cage-jump model thus enables to connect between H-bond dynamics and molecular diffusivity. arXiv:1903.06060v2 [cond-mat.soft]

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Section: Discussionmentioning

confidence: 99%

Diffusion dynamics of supercooled water modeled with the cage-jump motion and hydrogen-bond rearrangement

Kikutsuji

Kim

Matubayasi

2019

The Journal of Chemical Physics

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“…A key example is the selfdiffusion coefficient of water that exhibits a qualitative change moving across the Widom line at 1 bar by supercooling. [52][53][54] This has been measured in thin layers of water by Kimmel and co-workers 54 and it has been suggested that the data can be quantitatively described as, 52 ln…”

Section: An Open Challengementioning

confidence: 98%

Using Activation Energies to Elucidate Mechanisms of Water Dynamics

2021

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Recent advances in the calculation of activation energies are shedding new light on the dynamical time scales of liquid water. In this Perspective, we examine how activation energies elucidate the central, but not singular, role of the exchange of hydrogen-bond (H-bond) partners that rearrange the H-bond network of water. The contributions of other motions to dynamical time scales and their associated activation energies are discussed along with one case, vibrational spectral diffusion, where H-bond exchanges are not mechanistically significant. Nascent progress on outstanding challenges, including descriptions of non-Arrhenius effects and activation volumes, are detailed along with some directions for future investigations.

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“…The location of the liquid-liquid critical point although an important parameter of the model is a mere guess because of the two-state model being the mean-field approximation of phase transition. We localized it in 221.0 K and 53.5 MPa, which means that the critical pressure is little less than a minimum of 60 MPa expected by Ni et al 53 from a recent study of water diffusion. Most probably because of the less flexible LLTL and Widom line discussed above.…”

Section: Experimental Data the Touchstonementioning

confidence: 68%

Water above spinodal

Duška

2019

Preprint

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Liquid spinodal the bedrock of the water thermodynamics was for a long time discussed side by side with liquidliquid critical point elusively hidden beyond homogeneous nucleation limit inspiring numerous hypotheses aspiring to explain water anomalies. We combined these two concepts in their purest form creating a new equation of state capable of describing a real liquid. The equation expanding from the spinodal describes accurately the thermodynamic properties up to 100 MPa. We were able to predict spinodal in presence of liquid-liquid critical point and demonstrate that there is no such a feature as re-entering spinodal in water. It was predicted only because of the curved density surface caused by the existence of the second critical point. It practically excludes all other scenario except for the second critical point point at positive pressure. But critical point alone is not enough to capture the delicate shape of water; cooperativity the preference of nearby molecules to joint similar configurations proves to be important in the new equation. It designates water as a regular solution with phase separation driven not only by excess energy but also entropy. The heat capacity was also studied extensively making clear that disagreement between the two major experimental data sets available today is too profound. It could be explained only by additional underlying structural change. Because it is not present we can identify correct data.

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Communication: Diffusion constant in supercooled water as the Widom line is crossed in no man’s land

Abstract: Comment on "The putative liquid-liquid transition is a liquid-solid transition in atomistic models of water" [I and II: J.

Cited by 17 publications

References 60 publications

Diffusion dynamics of supercooled water modeled with the cage-jump motion and hydrogen-bond rearrangement

Diffusion dynamics of supercooled water modeled with the cage-jump motion and hydrogen-bond rearrangement

Using Activation Energies to Elucidate Mechanisms of Water Dynamics

Water above spinodal

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