Quantitative investigation of the two-state picture for water in the normal liquid and the supercooled regime

Accordino, Sebastián R.; Fris, J. A. Rodríguez; Sciortino, Francesco; Appignanesi, Gustavo A.

doi:10.1140/epje/i2011-11048-1

Cited by 58 publications

(81 citation statements)

References 42 publications

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“…Similar to the ab initio PBE0+TS-vdW(SC) simulations discussed above, the relative population of water molecules with I < 0.05Å 2 decreases by approximately 5% when the simulation temperature of the liquid is reduced from 330 K to 300 K using the TIP4P/Ice force field. Here, we note in passing that the dependence of P(I) on temperature has also been demonstrated with other classical water force fields [33][34][35] , yielding similar qualitative results to those observed in this work.…”

Section: A Lsi Distribution In Ambient Liquid Watersupporting

confidence: 87%

“…these small connected clusters may act as precursors for the growth of larger clusters of low-density-like molecules upon further cooling, a trend which was found in other theoretical studies [33][34][35] .…”

Section: Signature Of Polyamorphism In the Ipes Of Ambient Liquid supporting

confidence: 75%

“…Considering the fact that our IPES P(I) have a resolution of > 0.01Å 2 (due to the relatively low number of uncorrelated configurations accessed in our AIMD simulation), the position of this so-called isobestic point seems to be slightly dependent on these rather distinct ab initio and classical potentials. In this regard, previous studies of the IPES in liquid water based on classical force fields have reported that the position of this minimum is nearly invariant over a wide range of temperatures and pressures [33][34][35] . However, we note in passing that the position of the isobestic point is also weakly dependent on the choice of the cutoff distance used in Equation (1) to define the LSI distribution of radial distances 34 .…”

Section: B Lsi Distribution In the Inherent Potential Energy Surfacementioning

confidence: 87%

“…In this regard, previous studies of the IPES in liquid water based on classical force fields have reported that the position of this minimum is nearly invariant over a wide range of temperatures and pressures [33][34][35] . However, we note in passing that the position of the isobestic point is also weakly dependent on the choice of the cutoff distance used in Equation (1) to define the LSI distribution of radial distances 34 . In the IPES, we found that the relative heights of the two peaks in the bimodal P(I) distribution obtained with the PBE XC functional are significantly different than those obtained at the PBE0+TS-vdW(SC) level of theory.…”

Section: B Lsi Distribution In the Inherent Potential Energy Surfacementioning

confidence: 87%

“…In this regard, recent studies have shown that the local structure index (LSI) 31,32 is a very insightful order parameter that can be employed to characterize the LDL and HDL molecular environments 23 . For instance, the distribution of the LSI order parameter was found to be bimodal in the corresponding inherent potential energy surface (IPES) of both supercooled and ambient liquid water [33][34][35] . However, no attempt has been made yet to analyze the local environment in liquid water based on structures (configurations) generated using the more sophisticated ab initio based potentials available within the framework of density functional theory (DFT).…”

Section: Introductionmentioning

confidence: 99%

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Local structure analysis in ab initio liquid water

et al. 2015

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Within the framework of density functional theory, the inclusion of exact exchange and non-local van der Waals/dispersion (vdW) interactions is crucial for predicting a microscopic structure of ambient liquid water that quantitatively agrees with experiment. In this work, we have used the local structure index (LSI) order parameter to analyze the local structure in such highly accurate ab initio liquid water. At ambient conditions, the LSI probability distribution, P(I), was unimodal with most water molecules characterized by more disordered high-density-like local environments. With thermal excitations removed, the resultant bimodal P(I) in the inherent potential energy surface (IPES) exhibited a 3:1 ratio between high-and low-density-like molecules, with the latter forming small connected clusters amid the predominant population. By considering the spatial correlations and hydrogen bond network topologies among water molecules with the same LSI identities, we demonstrate that the signatures of the experimentally observed low-(LDA) and highdensity (HDA) amorphous phases of ice are present in the IPES of ambient liquid water. Analysis of the LSI autocorrelation function uncovered a persistence time of ∼ 4 ps-a finding consistent with the fact that natural thermal fluctuations are responsible for transitions between these distinct yet transient local aqueous environments in ambient liquid water.

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Section: A Lsi Distribution In Ambient Liquid Watersupporting

confidence: 87%

Section: Signature Of Polyamorphism In the Ipes Of Ambient Liquid supporting

confidence: 75%

Section: B Lsi Distribution In the Inherent Potential Energy Surfacementioning

confidence: 87%

Section: B Lsi Distribution In the Inherent Potential Energy Surfacementioning

confidence: 87%

Section: Introductionmentioning

confidence: 99%

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Local structure analysis in ab initio liquid water

et al. 2015

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Membrane Hydration

2015

Subcellular Biochemistry

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The book series SUBCELLULAR BIOCHEMISTRY is a renowned and well recognized forum for disseminating advances of emerging topics in Cell Biology and related subjects. All volumes are edited by established scientists and the individual chapters are written by experts on the relevant topic. The individual chapters of each volume are fully citable and indexed in Medline/Pubmed to ensure maximum visibility of the work.

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Hydration and Nanoconfined Water: Insights from Computer Simulations

Alarcón

Fris

Morini

et al. 2015

Subcellular Biochemistry

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The comprehension of the structure and behavior of water at interfaces and under nanoconfinement represents an issue of major concern in several central research areas like hydration, reaction dynamics and biology. From one side, water is known to play a dominant role in the structuring, the dynamics and the functionality of biological molecules, governing main processes like protein folding, protein binding and biological function. In turn, the same principles that rule biological organization at the molecular level are also operative for materials science processes that take place within a water environment, being responsible for the self-assembly of molecular structures to create synthetic supramolecular nanometrically-sized materials. Thus, the understanding of the principles of water hydration, including the development of a theory of hydrophobicity at the nanoscale, is imperative both from a fundamental and an applied standpoint. In this work we present some molecular dynamics studies of the structure and dynamics of water at different interfaces or confinement conditions, ranging from simple model hydrophobic interfaces with different geometrical constraints (in order to single out curvature effects), to self-assembled monolayers, proteins and phospholipid membranes. The tendency of the water molecules to sacrifice the lowest hydrogen bond (HB) coordination as possible at extended interfaces is revealed. This fact makes the first hydration layers to be highly oriented, in some situations even resembling the structure of hexagonal ice. A similar trend to maximize the number of HBs is shown to hold in cavity filling, with small subnanometric hydrophobic cavities remaining empty while larger cavities display an alternation of filled and dry states with a significant inner HB network. We also study interfaces with complex chemical and geometrical nature in order to determine how different conditions affect the local hydration properties. Thus, we show some results for protein hydration and, particularly, some preliminary studies on membrane hydration. Finally, calculations of a local hydrophobicity measure of relevance for binding and self-assembly are also presented. We then conclude with a few words of further emphasis on the relevance of this kind of knowledge to biology and to the design of new materials by highlighting the context-dependent and non-additive nature of different non-covalent interactions in an aqueous nanoenvironment, an issue that is usually greatly overlooked.

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Quantitative investigation of the two-state picture for water in the normal liquid and the supercooled regime

Cited by 58 publications

References 42 publications

Local structure analysis in ab initio liquid water

Local structure analysis in ab initio liquid water

Membrane Hydration

Hydration and Nanoconfined Water: Insights from Computer Simulations

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