The Spatial Structure in Liquid Water

Kusalik, Peter G.; Svishchev, Igor M.

doi:10.1126/science.265.5176.1219

Cited by 468 publications

(323 citation statements)

References 13 publications

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“…Such a model was apparently first put forward in literature in the known study [52] and then was developed in the works [53][54][55][56][57][58][59][60][61]. Within the framework of this approach it is possible to explain many anomalies of liquid water (it is possible to find details on the website [62]).…”

Section: The Mechanism Of Nucleation Of Bubstonsmentioning

confidence: 99%

Structure of the nanobubble clusters of dissolved air in liquid media

et al. 2011

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A qualitative model of the nucleation of stable bubbles in water at room temperature is suggested. This model is completely based on the property of the affinity of water at the nanometer scale; it is shown that under certain conditions the extent of disorder in a liquid starts growing, which results in a spontaneous decrease of the local density of the liquid and in the formation of nanometer-sized voids. These voids can serve as nuclei for the following generation of the so-called bubstons (the abbreviation for bubbles, stabilized by ions). The model of charging the bubstons by the ions, which are capable of adsorption, and the screening by a cloud of counter-ions, which are incapable of adsorption, is analyzed. It was shown that, subject to the charge of bubston, two regimes of such screening can be realized. At low charge of bubston the screening is described in the framework of the known linearized Debye-Huckel approach, when the sign of the counterion cloud preserves its sign everywhere in the liquid surrounding the bubston, whereas at large charge this sign is changed at some distance from the bubston surface. This effect provides the mechanism of the emergence of two types of compound particles having the opposite polarity, which leads to the aggregation of such compound particles by a ballistic kinetics.

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Section: The Mechanism Of Nucleation Of Bubstonsmentioning

confidence: 99%

Structure of the nanobubble clusters of dissolved air in liquid media

et al. 2011

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“…Only ∼6% of the H-bonded pairs in the bulk water (at cutoff of 2.65 Å) have intercalating waters. The intercalating waters represent a subgroup of the so-called fifth, interstitial, nontetrahedral, or mismatched water molecules (29,(48)(49)(50) that interact with the tagged water molecule by, predominantly, van der Waals forces. These water molecules are specific for liquid water and absent in ice.…”

Section: Ir Spectroscopy Of Water Molecules In the Neighborhood Of Pumentioning

confidence: 99%

Origin of hydrophobicity and enhanced water hydrogen bond strength near purely hydrophobic solutes

Grdadolnik

Merzel

Avbelj

2016

Proc. Natl. Acad. Sci. U.S.A.

201

145

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Hydrophobicity plays an important role in numerous physicochemical processes from the process of dissolution in water to protein folding, but its origin at the fundamental level is still unclear. The classical view of hydrophobic hydration is that, in the presence of a hydrophobic solute, water forms transient microscopic "icebergs" arising from strengthened water hydrogen bonding, but there is no experimental evidence for enhanced hydrogen bonding and/or icebergs in such solutions. Here, we have used the redshifts and line shapes of the isotopically decoupled IR oxygen-deuterium (O-D) stretching mode of HDO water near small purely hydrophobic solutes (methane, ethane, krypton, and xenon) to study hydrophobicity at the most fundamental level. We present unequivocal and model-free experimental proof for the presence of strengthened water hydrogen bonds near four hydrophobic solutes, matching those in ice and clathrates. The water molecules involved in the enhanced hydrogen bonds display extensive structural ordering resembling that in clathrates. The number of ice-like hydrogen bonds is 10-15 per methane molecule. Ab initio molecular dynamics simulations have confirmed that water molecules in the vicinity of methane form stronger, more numerous, and more tetrahedrally oriented hydrogen bonds than those in bulk water and that their mobility is restricted. We show the absence of intercalating water molecules that cause the electrostatic screening (shielding) of hydrogen bonds in bulk water as the critical element for the enhanced hydrogen bonding around a hydrophobic solute. Our results confirm the classical view of hydrophobic hydration.hydrophobic hydration | hydrogen bonding | IR spectroscopy | electrostatic screening | ab initio molecular dynamics D espite its great importance in numerous phenomena, the origin of hydrophobicity remains one of the most disputed topics in science (1-5). Experimental studies have shown that small purely hydrophobic solutes (alkanes and noble gases) in water increase the order (6, 7) and restrict the mobility (8) of neighboring water molecules. There are several opposing views on how to explain these data. The classical view is that a solute modifies water structure by forming transient, semiordered clathrate-like clusters ("icebergs"; used here only as a loose term) around it, arising from enhanced water hydrogen bonding (H bonding) (6, 7). This enhancement is brought about by either strengthening (9) or increasing the number of water to water H bonds (10). The classical view explains the characteristic changes in the thermodynamic variables of hydrophobic hydration (positive ΔG, ΔC p , negative ΔS, and ΔH) and the restricted mobility of water molecules observed by NMR (8). Neutron diffraction (11, 12) and extended X-ray absorption fine structure (EXAFS) (13) studies, however, show that the water molecules around small purely hydrophobic molecules do not differ significantly from those in pure liquid water. According to the dynamic view, the hydrophobic solute causes slowdown of t...

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“…All simulations have been done at 300 K temperature and 1 bar pressure. We have used the extended simple point charge model (SPC/E) [51,52] for water. We have treated the TBA molecules as united atoms, using the force field proposed by Lee and van der Vegt [47].…”

Section: Simulation Detailsmentioning

confidence: 99%

Fluctuating micro-heterogeneity in water–tert-butyl alcohol mixtures and lambda-type divergence of the mean cluster size with phase transition-like multiple anomalies

Banerjee

Furtado

Bagchi

2014

The Journal of Chemical Physics

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Water-tert-butyl alcohol (TBA) binary mixture exhibits a large number of thermodynamic and dynamic anomalies. These anomalies are observed at surprisingly low TBA mole fraction, with xTBA ≈ 0.03 − 0.07. We demonstrate here that the origin of the anomalies lies in the local structural changes that occur due to self-aggregation of TBA molecules. We observe a percolation transition of the TBA molecules at xTBA ≈ 0.05. We note that "islands" of TBA clusters form even below this mole fraction, while a large spanning cluster emerges above that mole fraction. At this percolation threshold, we observe a lambda-type divergence in the fluctuation of the size of the largest TBA cluster, reminiscent of a critical point. Alongside, the structure of water is also perturbed, albeit weakly, by the aggregation of TBA molecules. There is a monotonic decrease in the tetrahedral order parameter of water, while the dipole moment correlation shows a weak non-linearity. Interestingly, water molecules themselves exhibit a reverse percolation transition at higher TBA concentration, xTBA ≈ 0.45, where large spanning water clusters now break-up into small clusters. This is accompanied by significant divergence of the fluctuations in the size of largest water cluster. This second transition gives rise to another set of anomalies around. Both the percolation transitions can be regarded as manifestations of Janus effect at small molecular level.

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The Spatial Structure in Liquid Water

Cited by 468 publications

References 13 publications

Structure of the nanobubble clusters of dissolved air in liquid media

Structure of the nanobubble clusters of dissolved air in liquid media

Origin of hydrophobicity and enhanced water hydrogen bond strength near purely hydrophobic solutes

Fluctuating micro-heterogeneity in water–tert-butyl alcohol mixtures and lambda-type divergence of the mean cluster size with phase transition-like multiple anomalies

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