Water Nanodroplet Thermodynamics: Quasi-Solid Phase-Boundary Dispersivity

Zhang, Xi; Sun, Peng; Huang, Yongli; Ma, Zengsheng; Liu, Xinjuan; Zhou, Ji; Zheng, Weitao; Sun, Chang Q.

doi:10.1021/acs.jpcb.5b00773

Cited by 28 publications

(21 citation statements)

References 50 publications

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“…Therefore, nanodroplets, nanobubbles, and water ice skins undergo simultaneously T N depression and T m elevation, and the extent of dispersion varies with the fraction of undercoordinated molecules of the object. 42 The Journal of Physical Chemistry C Article and compresses the η L (T) curve, which disperses the extremedensity temperatures. A bubble is just the inversion of a droplet; a hollow sphere like a soap bubble contains two skinsthe inner and the outer.…”

Section: Thermodynamics Of Undercoordinatedmentioning

confidence: 99%

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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Section: Thermodynamics Of Undercoordinatedmentioning

confidence: 99%

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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“…the repulsive force between the H-O bonding electrons and the O:H nonbonding pair within a O:H-O bond, should play a significant role in various anomalies of water and ice, such as extraordinary recoverability, skin lubricity, etc 33343536…”

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confidence: 99%

“…For example, in the temperature range from 250 K to 277 K, H-O covalent bond exhibit the normal thermal expansion, while O:H nonbond shrinks due to the reducing repulsive force, leading to the contraction of the total O–O distance3436. At the skin of ice, due to the decrease of the molecular coordination, H-O covalence bond contracts spontaneously to lower the cohesive energy, and hence O:H nonbond is polarized, leading to the surface lubricity3537. This force is beyond the conventional intra- and inter-molecular interactions but depending on the existence of the O:H-O link, i.e.…”

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confidence: 99%

Hydrogen-bond potential for ice VIII-X phase transition

Zhang

Chen

2016

Sci Rep

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Repulsive force between the O-H bonding electrons and the O:H nonbonding pair within hydrogen bond (O-H:O) is an often overlooked interaction which dictates the extraordinary recoverability and sensitivity of water and ice. Here, we present a potential model for this hidden force opposing ice compression of ice VIII-X phase transition based on the density functional theory (DFT) and neutron scattering observations. We consider the H-O bond covalent force, the O:H nonbond dispersion force, and the hidden force to approach equilibrium under compression. Due to the charge polarization within the O:H-O bond, the curvatures of the H-O bond and the O:H nonbond potentials show opposite sign before transition, resulting in the asymmetric relaxation of H-O and O:H (O:H contraction and H-O elongation) and the H+ proton centralization towards phase X. When cross the VIII-X phase boundary, both H-O and O:H contract slightly. The potential model reproduces the VIII-X phase transition as observed in experiment. Development of the potential model may provide a choice for further calculations of water anomalies.

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“…(4) Does a solid skin form on water or a liquid sheet cover ice? [2] and dispersion of the quasisolid phase boundaries [6]. b A video clip [7] shows that a water droplet bounces continuously on a flat water surface, which evidences the elasticity and hydrophobicity of both skins.…”

Section: Challenge: Why Is Water Skin Unusual?mentioning

confidence: 99%

Water Supersolid Skin

Sun

2016

Springer Series in Chemical Physics

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Skin molecular undercoordination not only disperses the quasisolid phase boundary but also derives supersolidity that is hydrophobic, less dense, viscoelastic, repulsive, and thermally stable.• The supersolidity and quasisolidity defines the anomalies of water skin when interact with other objects. • The skin supersolidity increases with its curvature but drops when heated due to depolarization. • Electrostatic repulsivity and elasticity claims the superhydrophobicity, superfluidity, superlubricity, and supersolidity at the contacting interface.Abstract Consistency in experimental observations, numerical calculations, and theoretical predictions revealed that skins of 25°C water and −(15-20)°C ice share the same attribute of supersolidity characterized by the identical H-O vibration frequency of 3450 cm −1 . Molecular undercoordination and inter-electron-pair repulsion shortens the H-O bond and lengthen the O:H nonbond, leading to a dual process of nonbonding electron polarization. This relaxation-polarization process enhances the dipole moment, elasticity, viscosity, thermal stability of these skins with 25 % density loss, which is responsible for the hydrophobicity and toughness of water skin and the superfluidity in a microchannel.

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Water Nanodroplet Thermodynamics: Quasi-Solid Phase-Boundary Dispersivity

Cited by 28 publications

References 50 publications

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

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

Hydrogen-bond potential for ice VIII-X phase transition

Water Supersolid Skin

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Water Nanodroplet Thermodynamics: Quasi-Solid Phase-Boundary Dispersivity

Cited by 28 publications

References 50 publications

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

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

Hydrogen-bond potential for ice VIII-X phase transition

Water Supersolid Skin

Contact Info

Product

Resources

About

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

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