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The notion of asymmetrical Hydrogen Bond (O:H-O) Cooperativity and Polarizability (HBCP) has enabled exploration of the core physics behind irregularities of water and ice, particularly, the evolution of mass density, phase stability, energy exchange, and their transition velocity under perturbation. We humbly share the initiatives of the quasisolidity presented between Liquid and Ice, the supersolidity pertained to polarization by electrification or molecular undercoordination, and the H ↔ H and O: ⇔ :O repulsivity owing to the respective injection of excessive protons and lone pairs to the liquid by solvation. The O—O repulsivity forms the key that drives the O:H-O bond to cooperatively relax its segmental length, cohesive energy, vibration frequency, and specific heat upon perturbation, which establishes an efficient set of parameters to feature the bonding and electronic dynamics in the frequency–space–time domains. An interplay of the segmental specific heats defines the mass densities, phase boundaries, and the exotic quasisolid (QS) phase that exhibits negative thermal expansivity through H-O contracting less than the scale of O:H expansion upon cooling. However, the H-O bond undergoes cooling elongation in the Liquid and the Ice-I phase and remains silent in the XI phase. H-O bond absorbs energy by contraction and does it inverse at expansion. The O:H nonbond always relaxes more than the H-O bond does in contrasting direction. Mechanical compression symmetrizes the O:H-O segmental length associated with polarization, which disperses inwardly the QS phase boundary to lower the T m for melting but raise the temperature T N for ice nucleation and the T V for evaporation, resulting in the phenomena of ice regelation and instant-ice formation. Polarization, however, has the contrast effect to compression on the hydrogen bond relaxation and phase transition. The polarization converts the pristine water into the gel-like, hydrophobic, and viscoelastic supersolid which is less-dense and thermally more diffusive and stable, entitling surface premelting, superheating at T m , and supercooling at T N and T V. Polarization enhances the dielectrics of water and widens the bandgap of ice. The supersolidity ensures the 120 K superelasticity of ice microfibers and the 330 K stability of the electrified water bridge crossing the rims of infilled containers. The high elasticity of the softer O:H nonbond and the interface electrostatic repulsivity secure the slipperiness of ice and the superfluidity of water traveling in fine channels. The skin supersolidity and the O:H-O bond memorability uniquely foster the Mpemba effect — warm water cools more quickly. The H ↔ H or O: ⇔ :O repulsivity modifies the bonding network and solution properties through solvent H-O bond elongation, solute H-O bond contraction, and polarization. The HBCP premise has thus correlated the irregularity of water and ice to the O:H-O bonding and electronic dynamics under perturbation. Further extension of the HBCP to aqueous and molecular assemblies involved with electron lone pairs and coupling interactions could be even more fascinating and profoundly promising. [Display omitted] • O—O repulsive coupling interaction entitles the irregularity of water and ice. • O:H-O bond cooperativity and polarizability revolutionizes the parameter space. • Perturbations drive the quasisolidity, supersolidity, H ↔ H and O: ⇔ :O repulsivity. • Specific-heat disparity resolves water's density anomalies and phase boundaries. • The T m and T N /T V vary respectively with the H-O and the O:H binding energy. • (e; ± ;H 3 O + ;HO −) ⋅ 4H 2 O:6H 2 O hydration revises solution's network and properties. [ABSTRACT FROM AUTHOR]

Aqueous charge injection in forms of electrons, protons, lone pairs, ions, and molecular dipoles by solvation is ubiquitously important to our health and life. Pursuing fine-resolution detection and consistent insight into solvation dynamics and solute capabilities has become an increasingly active subject. This treatise shows that charge injection by solvation mediates the O:H-O bonding network and properties of a solution through O:H formation, H↔H fragilization, O:⇔:O compression, electrostatic polarization, H2O dipolar shielding, solute-solute interaction, and undercoordinated H-O bond contraction. A combination of the hydrogen bond (O:H-O or HB with ':' being the electron lone pairs of oxygen) cooperativity notion and the differential phonon spectrometrics (DPS) has enabled quantitative information on the following: (i) the number fraction and phonon stiffness of HBs transiting from the mode of ordinary water to hydration; (ii) solute-solvent and solute-solute molecular nonbond interactions; and (iii) interdependence of skin stress, solution viscosity, molecular diffusivity, solvation thermodynamics, and critical pressures and temperatures for phase transitions. An examination of solvation dynamics has clarified the following: (i) the excessive protons create the H↔H or anti-HB point breaker to disrupt the acidic solution network and surface stress. (ii) The excessive lone pairs generate the O:⇔:O or super-HB point compressor to shorten the O:H nonbond but lengthen the H-O bond in H2O2 and basic solutions; yet, bond-order-deficiency shortens and stiffens the H-O bond due H2O2 and OH− solutes. (iii) Ions serve each as a charge center that aligns, clusters, stretches, and polarizes their neighboring HBs to form hydration shells. (iv) Solvation of alcohols, aldehydes, complex salts, carboxylic and formic acids, glycine, and sugars distorts the solute-solvent interface structures with the involvement of the anti-HB or the super-HB. Extending the knowledge and strategies to catalysis, solution-protein, drug-cell, liquid-solid, colloid-matrix interactions and molecular crystals would be even more fascinating and rewarding. [ABSTRACT FROM AUTHOR]

The resultant energy of solvent H–O bond exothermic elongation by O:⇔:O repulsion, featured at <3100 cm −1 , and the solute H–O bond endothermic contraction by bond-order-deficiency, at 3610 cm −1 , heats up the (Li, Na, K)OH solutions. The solution temperature increases linearly with the number fraction of the ordinary O:H–O bonds transiting into their hydration states. The elongated H–O bond emits >150% the O:H cohesive energy of 0.095 eV that caps the energy dissipating by molecular motion, thermal fluctuation, diffusion, and even evaporation. Therefore, the intramolecular H–O bond relaxation dictates the OH − solvation bonding thermodynamics and the performance of basic solutions. [ABSTRACT FROM AUTHOR]

Energy density and structure stability are of key concerns in devising energy materials such as CNHO molecular crystals and the emerging cyclo-N 5 − complexes for desired explosive functionalities with a mechanism being open for exploration. An extension of the recent progress in solvation suggests that a combination of the intermolecular hydrogen bond (X:H–Y or HB with ':' being electron lone pair of X, Y = O or N) tension and the super-HB (X:⇔:Y) or anti-HB (H↔H) compression not only stabilizes the structure but also stores excessive energy by shortening the intramolecular bonds. The presence of the X:H constrains and the presence of the X:⇔:Y and/or H↔H fosters the explosion. Observations suggest that the absence of X:H–Y tension results in the spontaneous aquatic explosion of alkali metals and molten alkali halides. The lack of X:⇔:Y repulsion fosters no explosion of the molten NaCl in liquid NH 3 , nor the molten Na 2 CO 3 salt or H 3 BO 3 acid in water. The findings shall offer guidelines for devising efficient energy materials and reconciling the nature origin of water ice, aqueous solutions, and explosive energy materials – significance of electron lone pairs and protons. The combination of the hydrogen-bond (X:H–Y) tension and the super-HB (X:⇔:Y) or the anti-HB (H↔H) repulsion not only stabilizes the structure but also stores energy by shortening the intramolecular covalent bonds. The X:H tension constrains and the X:⇔:Y repulsion fosters explosion. Unlabelled Image • Segmental cooperativity of the X:H-Y oscillator pair dictates the behavior of aqueous solutions. • Excessive H+ or lone pairs ":" derive H↔H or X:⇔:Y repulsion in molecular crystals/liquids. • X:⇔:Y or/and H↔H repulsion and X:H-Y tension governs the stability and energy of crystals. • The absence/presence of the X:H-Y tension fosters the spontaneous/constrained explosion. [ABSTRACT FROM AUTHOR]

An incorporation of the hydrogen bond (O:H O or HB) cooperativity notion, contact angle detection, and the differential phonon spectrometrics (DPS) has enabled us to gain refined information on the HCl, KCl and KOH solvation resolved solute-solvent molecular interactions and the solution surface stresses. Results show that ionic polarization stiffens the solvent H O bond phonon from 3200 to 3480 cm −1 in the hydration shells. The HO − in alkaline solution, however, shares not only the same H O phonon redshift of compressed water from 3200 to < 3100 cm −1 but also the dangling bonds of H 2 O surface featured at 3610 cm −1 . Salt and alkaline solvation enhances the solution surface stress by K + and Cl − ionic polarization. The excessive H + proton in acid solution forms a H↔H anti-HB that depresses the solution surface stress, instead. The solute capability of transforming the fraction of the O:H O bonds of the solvent matrix is featured by: f H = 0 and f x ∝ 1-exp(-C/C 0 ) (x = HO − , K + and Cl − ) towards saturation. Exercises not only confirm the presence of the H↔H anti-HB point fragilization, the O:⇔:O super-HB point compression, and ionic polarization dominating the performance of the respective HCl, KOH, and KCl solutions, but also demonstrate the power of the DPS that enables high resolution of solute-solute-solvent interactions and correlation between HB relaxation and solution surface stress. [ABSTRACT FROM AUTHOR]

[Display omitted] • Hydration dissolves an organic trunk into molecular dipoles wrapped with lone pairs and protons. • Solute interacts with solvent via O:H attraction, H ↔ H and O:⇔:O repulsion, with polarization. • Polarization shortens and stiffens the H-O but the O:H responses to polarization contrastingly. • Repulsion disrupts the bonding network and surface stress by fragmentation of the solution. Interaction between an organic molecular solute and its hydrating H 2 O molecules is of great importance to processes varying from cryopreservation, denaturation of protein and DNA, and drug-cell interaction, to chemical, healthcare, and food and pharmaceutical sciences and technologies. However, the nature and functionality of the interfacial states, at the sub-molecular level, are particularly poorly known. On the views of solvation charge injection, electronic polarization, and bonding network disruption, we show experimental evidence for the interfacial supersolidity and its functionality on the performance of solutions. The asymmetrically distributed lone pairs and protons of the molecular solute interact with their unlike or alike of its hydrating H 2 O molecules to initiate the O:H attraction, H ↔ H repulsion or O:⇔:O compression associated with the molecule dipolar polarization, and solute–solute repulsion, without involvement of charge sharing or regular bond formation. Polarization lengthens the hydrating O:H and shortens the H-O, and repulsion does however the partitioned O:H-O bond contrastingly, which not only enriches the THz phonons but also results in the interfacial supersolidity characterized at H-O oscillating frequency ∼3450 cm−1. Solvation investigation of acids, alcohols, aldehydes, glycines, and sugars confirmed the prediction of the interfacial supersolidity and estimation of hydration cell size and the involvement of solute–solute repulsion. The solute dipolar polarizability distorts and the interfacial H ↔ H or O:⇔:O repulsivity disrupts the hydrogen bonding network. The bond relaxation, polarization, structure distortion, and network disruption modulate the hydrophilicity, surface stress, solubility, and solution viscosity. Findings not only improve the comprehension of the dynamics of molecular hydration and the functionality of the solutions but also offer efficient spectral means for identification and quantification of the interfacial hydration cell size and its supersolidity. [ABSTRACT FROM AUTHOR]

Raman phonon differential spectrometrics (DPS) and contact angle measurements resolved that solvation of the NaX (X = HSO 4 , NO 3 , ClO 4 , SCN) complex salts stiffens the H O stretching phonon from 3200 to ~ 3500 cm − 1 and softens the O:H nonbond phonon from 180 to ~ 70 cm − 1 with rising of solution surface stress. The solute capability of bond transition in terms of the fraction coefficient, follows the relation, f NaX (C) ∝ 1-exp(− C/C 0 ) towards saturation, with C being the solute concentration and C 0 the decay constant. Observations evidence that: (i) the solute ionic field electrification aligns, stretches, and polarizes its neighboring H 2 O molecules, which shortens the H O bond but lengthens the O:H nonbond via O O Coulomb repulsion; (ii) the effect of X − electrification on the O:H O bond relaxation varies with solute type and solute concentration. Exercises not only verify the essentiality of solvent O:H O bond cooperative relaxation and polarization but also demonstrate the power of DPS that resolves processes occurred upon solvation. [ABSTRACT FROM AUTHOR]

Low-temperature Raman spectroscopy revealed that sugar solvation depresses the critical temperature for homogeneous ice nucleation ( T N ) whose depression extent follows the order of: trehalose > glucose > fructose at the same concentration and the extent of T N depression for a specific sugar is proportional to its concentration. We attribute the T N depression to the O:H vibration mode redshift induced by the solute dipolar polarization and distortion of the solvent hydrogen bond (O:H O or HB with “:” being the electron lone air of oxygen). The O:H phonon redshift lowers the Debye temperature of the O:H specific heat and disperses the quasisolid-phase boundary and the associated T N . [ABSTRACT FROM AUTHOR]

Solvation of acid, base, and salt is ubiquitously important to all subject areas in chemistry, health care and life science. However, fine resolution of the solvation dynamics, solute-solvent molecular interactions, and solute capability of transforming the hydrogen bond (O:H O, or HB) and surface stress remain great challenge. Incorporating the notion of O:H O bond cooperativity with a strategy of differential phonon spectroscopy (DPS) has enabled resolution on the fraction and stiffness of the solvent HB from the mode of water to the hydration shells upon NaOH, NaI and HI solvation. Results show that Na + and I + ionic polarization shortens the H O bond and stiffens its phonon from 3200 to 3500 cm − 1 in the hydration shells. The H + in the HI solution forms a H ↔ H anti-HB that disrupts the solution network and surface stress. The excessive electron lone pairs of OH – form the O : ⇔ : O super-HB that compresses the network, sharing the same effect of mechanical compression shifting the H O phonon from above 3100 cm − 1 to its below; the solute H O bond performs the same to the H O dangling bond at surface featured at 3610 cm − 1 . The fraction coefficients or phonon abundance transition, f H = 0, f HO ∝ C, and f x ∝ 1-exp(− C/C 0 ) (x = Na + and I − and C the solute concentration) towards saturation, feature the solute capability of HB transformation. Practice not only confirms the essentiality of the H ↔ H anti-HB point fragilization, the O : ⇔ : O super-HB point compression, and the ionic polarization to the performance of the respective HI, NaOH, and NaI solutions, but also demonstrate the power of the DPS that enables fine-resolution of solvation dynamics and solute capabilities. [ABSTRACT FROM AUTHOR]

A combination of the differential Raman spectrometrics and contact-angle measurements has enabled resolution of the hydrogen bond (HB, O:H O) relaxation and molecular dynamics in the NaX hydration shells. Observations suggest that the aqueous ions create each an electric field to form the hydration shells through O:H O bond elongation and polarization. The ionic polarization shares the same, and even stronger, effect of molecular undercoordination that shortens the H O bond and stiffen its phonon, and meanwhile, the O O Coulomb repulsivity lengthen and soften the O:H nonbond with an association of polarization. O:H O bond electrification raises not only the structure order of molecules and the viscosity in the hydration shells but also the skin stress and thermal stability of the solution. Exercises not only deepen our insight into the salt solute-solvent interaction involved in the Hofmeister series in terms of O:H O bond electrification but also provide a powerful means quantifying the dynamic, local, molecular-site-resolved information regarding the O:H O bond cooperativity in aqueous solutions. [ABSTRACT FROM AUTHOR]

Perturbation Raman spectroscopy has underscored the hydrogen bond (O:H–O or HB) cooperativity and polarizability (HBCP) for water, which offers a proper parameter space for the performance of the HB and electrons in the energy-space-time domains. The O O repulsive coupling drives the O:H–O segmental length and energy to relax cooperatively upon perturbation. Mechanical compression shortens and stiffens the O:H nonbond while lengthens and softens the H O bond associated with polarization. However, electrification by an electric field or charge injection, or molecular undercoordination at a surface, relaxes the O:H–O in a contrasting way to the compression with derivation of the supersolid phase that is viscoelastic, less dense, thermally diffusive, and mechanically and thermally more stable. The H O bond exhibits negative thermal expansivity in the liquid and the ice-I phase while its length responds in proportional to temperature in the quasisolid phase. The O:H–O relaxation modifies the mass densities, phase boundaries, critical temperatures and the polarization endows the slipperiness of ice and superfluidity of water at the nanometer scale. Protons injection by acid solvation creates the H↔H anti-HB and introduction of electron lone pairs derives the O:⇔:O super-HB into the solutions of base or H 2 O 2 hydrogen-peroxide. The repulsive H↔H and O:⇔:O interactions lengthen the solvent H O bond while the solute H O bond contracts because its bond order loss. Differential phonon spectroscopy quantifies the abundance, structure order, and stiffness of the bonds transiting from the mode of pristine water to the perturbed states. The HBCP and the perturbative spectroscopy have enabled the dynamic potentials for the relaxing O:H–O bond. Findings not only amplified the power of the Raman spectroscopy but also substantiated the understanding of anomalies of water subjecting to perturbation. Scaling relations for the HBCP of the (a) measured segmental length and the (b) computed H O vibration frequency. [Display omitted] • O O repulsion couples the intramolecular H O and intermolecular O:H interactions. • O:H–O segmental length, energy, frequency, and specific heat parameterize water ice. • Mechanical compression shortens the O:H and lengthens the H O and polarizes water. • Electrification or molecular undercoordination effects contrastingly to compression. • DPS distills the abundance-order-stiffness transition of O:H–O driven by perturbation. [ABSTRACT FROM AUTHOR]

The H N bond in the TATB assembly exhibits excitingly negative compressibility and negative thermal expansivity because of the unprecedented O N coupling interactions. [Display omitted] • O:H N bond in TATB acts the same to O:H O in H 2 O upon compression and heating. • H N bond possesses negative compressibility and negative thermal expansibility. • Heating shortens C NH 2 and N H but does the C NO 2 and N O contrastingly. • The O/N:H nonbonds possess the regular compressibility and thermal expansivity. • The N O repulsion drives the unusual response of the O:H N bond to perturbation. Incorporating the mechanical and thermal perturbations to the Raman spectroscopy has enabled resolution to the response of the individually segmented C N 2H:2O N C interactions for the 1,3,5-triamona, 2,4,6-trinitorbenzene (TATB, C 6 H 6 N 6 O 6) assembly with ":" representing the electron lone pair of nitrogen or oxygen at the molecular interfaces. It is uncovered that: (i) the N H bond possesses the negative compressibility and negative thermal expansivity; (ii) the C (N 2H) bond undergoes both compressive and thermal contraction; (iii) the (O,N):H and rest interactions follow the regular compressibility and thermal expansivity. The unusual response of the H N bond in TATB to perturbation is the same to the H O segment of the O:H O bond of water ice and the N:H O bond of the cyclo -N 5 −:4H 3 O+ complexes, which proves that the O:⇔:N repulsion couples the inter-(O:H) and the intramolecular (H N) interactions and drives the O:H N to relax cooperatively in the segmental length, energy, and vibration frequency when subjecting to perturbation. Discoveries demonstrate not only the significance of molecular coupling interactions but also the power of mechanical and thermal perturbations that enable detailed information of individual bond relaxation, advancing the engineering in chemistry and devising of functional molecular materials. [ABSTRACT FROM AUTHOR]

[Display omitted] • An ion forms a supersolid hydration cell by screened polarization of H 2 O dipoles. • Ionic polarization shortens and stiffens the H-O while does the O:H contrastingly. • A cation keeps its hydration volume invariant without being interfered by others. • Inter-anion repulsion reduces anionic hydration volume by weakening its field. • Cation/anion polarizability governs the linear/nonlinear term of Jones-Dale viscosity. Understanding the performance of individual ions in salt solutions and the consequence of ionic hydration on hydrogen bonding network distortion, surface stress, and solution viscosity remains great challenge. We show herein findings pertained to alkali halide YX solutions using differential phonon spectroscopy (X = Cl, Br, I; Y = Li, Na, K, Rb, Cs): (i) an ion occupies eccentrically the tetrahedrally-coordinated interstitial of water to form a (±:4H 2 O:6H 2 O) hydration cell without bonding to H 2 O molecules; (ii) ionic polarization shortens and stiffens the H-O bond while does the O:H nonbond contrastingly; (iii) the screening of the hydrating water dipoles limits the cation hydration cell to be size invariant while the inter-anion repulsion reduces its hydration volume by weakening the anionic long-range electric field when the ionic separation shrinks; and (iv) the polarization of cation and anion dictates respectively the linear and the nonlinear part of Jones-Dale's viscosity and surface stress. Findings would provide profound impact to the understanding and deep engineering of water, ice, and aqueous solutions. [ABSTRACT FROM AUTHOR]

[Display omitted] • A 5775 defect was uncovered in the interlocked bilayer ice. • Calculations confirmed the stability of 5775 defect. • The 5775 defect tends to form during ice growth other than by postgrowth reaction. • The defect does not break the four-coordinate H-bond structure. A localized, metastable, 5775-type defect is uncovered in the double-layer ice with and without Au(1 1 1) support from density functional theory calculations. Without destroying the total number conservation of the hydrogen bonds in the hexagonal ice, the defect only dislocates the molecules by 0.08 Å associated with a 3.27% difference of the interaction energy. The high energy barrier, low quantum tunneling and thermal transporting probabilities hindered the transformation from the 6666 to the 5775 structures. This finding indicates that the defected ice is stable, and it tends to form during the ice growth instead of post-grown process. [ABSTRACT FROM AUTHOR]

A set of concepts cultivated in the past decade has substantiated the understanding of water ice compression. The concepts include the coupled hydrogen bond (O:H–O) segmental cooperativity, segmental specific-heat disparity, compressive O:H–O symmetrization and polarization, and quasisolidity. Computational and spectrometric outcome consistently justifies that the intromolecular H–O bond has a negative compressibility while the intermolecular O:H nonbond does contrastingly because of the involvement of the interionic O O repulsive coupling. Compression lowers the melting point T m (named regelation) and raises the freezing temperature T N (for instant ice formation) by inward shifting the quasisolid phase boundary through Einstein's relation, ΔΘ Dx ∝ Δ ω x , which is in contrast to the effects of electrostatic polarization and water molecular undercoordination. Theoretical reproduction of the phase boundaries in the phase diagram revealed that H–O bond relaxation dictates boundaries of negative slope, d T C /d P < 0, and that the O:H relaxation determines those of d T C /d P > 0. O:H–O bond frozen governs boundaries of constant T C such as the I C -XI boundary and the H–O and O:H energy compensation yields those of constant P C such as X-VII/VIII boundaries. The O O repulsion opposes compression minimizing the compressibility. Polarization enlarges the bandgap and the dielectric permittivity of water ice by raising the nonbonding states above the Fermi energy. Progress evidences the efficiency and essentiality of the coupled O:H–O bonding and electronic dynamics in revealing the core physics and chemistry of water ice, which could extend to other molecular crystals such as energetic materials. • O O repulsion minimizes the compressibility and polarization governs the viscosity. • Lone pair polarization widens the bandgap and raises the dielectric permittivity. • O:H or H–O relaxation discriminates phase boundaries according to their dT/dP slopes. • H–O energy governs the T m while the O:H dictates the freezing T N and vaporization T V. [ABSTRACT FROM AUTHOR]