Perturbative vibration of the coupled hydrogen-bond (O:H-O) in water.

ABSTRACT

Perturbation Raman spectroscopy has underscored the hydrogen bond (OH-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 OO repulsive coupling drives the OH-O segmental length and energy to relax cooperatively upon perturbation. Mechanical compression shortens and stiffens the OH nonbond while lengthens and softens the HO bond associated with polarization. However, electrification by an electric field or charge injection, or molecular undercoordination at a surface, relaxes the OH-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 HO 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 OH-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 H2O2 hydrogen-peroxide. The repulsive H↔H and O⇔O interactions lengthen the solvent HO bond while the solute HO 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 OH-O bond. Findings not only amplified the power of the Raman spectroscopy but also substantiated the understanding of anomalies of water subjecting to perturbation.