Communication: Long-range angular correlations in liquid water

Liu, Yu; Wu, Jianzhong

doi:10.1063/1.4817321

Cited by 31 publications

(36 citation statements)

References 22 publications

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“…The maps show unambiguously that the structures are much better defined than one might have expected from the small values of the excess entropy. Therefore, there is a correlation between an angular magnitude and both the g OO (r) and S trans (r), contrary to the results of earlier studies 12 .…”

Section: Resultscontrasting

confidence: 57%

The structure of liquid water beyond the first hydration shell

Henao

Büsch

Guàrdia

et al. 2016

Phys. Chem. Chem. Phys.

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There is to date a general consensus on the structure of the first coordination shells of liquid water, namely a tetrahedral short range order of the molecules. In contrast, little is known about the structure at longer distances and the influence of the tetrahedral molecular arrangement of the first shells on the order at these length scales. An expansion of the distance dependent excess entropy is used in this contribution to find out which molecular arrangements are important at each distance range. This was done by splitting the excess entropy into two parts: one connected to the relative position of two molecules, and the other one related to their relative orientation. A transition between two previously unknown regimes in liquid water is identified at a distance of about ∼6 Å: from a predominantly orientational order at shorter distances to a regime at larger distances of up to ∼9 Å where the order is predominantly positional and molecules are distributed with the same tetrahedral symmetry as the very first molecules.

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Section: Resultscontrasting

confidence: 57%

The structure of liquid water beyond the first hydration shell

Henao

Büsch

Guàrdia

et al. 2016

Phys. Chem. Chem. Phys.

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“…It is always positive in solute free water and decays in an oscillatory manner. The characteristics of this function are closely shared by another long range angular correlation function computable using classical density functional theory calculations 25 , further strengthening the likely existence of long range orientationally correlated domains of water molecules. It has been suggested from HRS observations that long range orientational correlations in molecular liquids are expressed through propagating waves in molecular reorientation instead of diffusional orientation of molecules 43 .…”

Section: B Effect Of Salts On Longitudinal Correlationsmentioning

confidence: 60%

Effect of simple solutes on the long range dipolar correlations in liquid water

Baul

Anishetty

Vemparala

2016

The Journal of Chemical Physics

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Intermolecular correlations in liquid water at ambient conditions have generally been characterized through short range density fluctuations described through the atomic pair distribution functions. Recent numerical and experimental results have suggested that such a description of order or structure in liquid water is incomplete and there exist considerably longer ranged orientational correlations in water that can be studied through dipolar correlations. In this study, using large scale classical, atomistic molecular dynamics simulations using TIP4P-Ew and TIP3P models of water, we show that salts such as sodium chloride (NaCl), potassium chloride (KCl), caesium chloride (CsCl), and magnesium chloride (MgCl2) have a long range effect on the dipolar correlations, which cannot be explained by the notion of structure making and breaking by dissolved ions. Observed effects are explained through orientational stratification of water molecules around ions and their long range coupling to the global hydrogen bond network by virtue of the sum rule for water. The observations for single hydrophilic solutes are contrasted with the same for a single methane (CH4) molecule. We observe that even a single small hydrophobe can result in enhancement of long range orientational correlations in liquid water, contrary to the case of dissolved ions, which have been observed to have a reducing effect. The observations from this study are discussed in the context of hydrophobic effect.

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“…Numerical reproduction of the T m (P) profiles 66 indicates that the T m is proportional to E H , and Figure 4a suggests that the T N be proportional to E L . In order to minimize calculation artifacts, a modification of the ω L (N) curve in Figure 2b is made with respect to the measured value of 220 cm −1 for bulk water and to that the calculated ω x matches the measured value at N = 2.…”

Section: Thermodynamics Of Undercoordinatedmentioning

confidence: 98%

Potential Paths for the Hydrogen-Bond Relaxing with (H₂O)_N Cluster Size

Huang

Zhang

et al. 2015

J. Phys. Chem. C

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Relaxation of the hydrogen bond (O:H−O) between oxygen ions of undercoordinated molecules fascinates the behavior of water nanodroplets and nanobubbles. However, probing such potentials remains yet far from reality. Here we show that the Lagrangian solution (Huang et al. J. Phys. Chem. B 2013, 117, 13639) transforms the observed H−O bond (x = H) and O:H nonbond (x = L) lengths and their characteristic phonon frequencies (d x , ω x ) (Sun et al. J. Phys. Chem. Lett. 2013, 4, 2565) into their respective force constants and cohesive energies (k x , E x ), which results in mapping of the potential paths for the O:H−O bond relaxing with (H 2 O) N cluster size. Results show that molecular undercoordination not only reduces its size (H−O length d H ) with enhanced H−O energy from the bulk value of 3.97 to 5.10 eV for a H 2 O monomer but also enlarges their separation (O:H distance d L ) with O:H energy reduction from 95 to 35 meV for a dimer. The H−O energy gain raises the melting point of water skin from the bulk value 273 to 310 K, and the O:H energy loss lowers the freezing temperature of a 1.4 nm sized droplet from the bulk value 258 to 202 K, which indicates droplet size induced dispersion of the quasisolid phase boundaries.

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Communication: Long-range angular correlations in liquid water

Cited by 31 publications

References 22 publications

The structure of liquid water beyond the first hydration shell

The structure of liquid water beyond the first hydration shell

Effect of simple solutes on the long range dipolar correlations in liquid water

Potential Paths for the Hydrogen-Bond Relaxing with (H₂O)_N Cluster Size

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Communication: Long-range angular correlations in liquid water

Cited by 31 publications

References 22 publications

The structure of liquid water beyond the first hydration shell

The structure of liquid water beyond the first hydration shell

Effect of simple solutes on the long range dipolar correlations in liquid water

Potential Paths for the Hydrogen-Bond Relaxing with (H2O)N Cluster Size

Contact Info

Product

Resources

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Potential Paths for the Hydrogen-Bond Relaxing with (H₂O)_N Cluster Size