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Intermolecular Forces03:13

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Atoms and molecules interact through bonds (or forces): intramolecular and intermolecular. The forces are electrostatic as they arise from interactions (attractive or repulsive) between charged species (permanent, partial, or temporary charges) and exist with varying strengths between ions, polar, nonpolar, and neutral molecules. The different types of intermolecular forces are ion–dipole, dipole–dipole, hydrogen bonds, and dispersion; among these, dipole–dipole, hydrogen...
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The ionic association is the association of oppositely charged ions in an electrolyte solution to form ion pairs. Bjerrum defined ion pairs as two oppositely charged ions whose electrostatic attraction exceeds the thermal energy of the system, typically expressed as 2kT. Electrostatic attraction depends on ionic charge, separation distance, and the dielectric constant of the medium. Thermal energy, represented by kT, reflects the tendency of ions to move independently due to molecular motion.
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NMR-active nuclei have energy levels called 'spin states' that are associated with the orientations of their nuclear magnetic moments. In the absence of a magnetic field, the nuclear magnetic moments are randomly oriented, and the spin states are degenerate. When an external magnetic field is applied, the spin states have only 2 + 1 orientations available to them. A proton with = ½ has two available orientations. Similarly, for a quadrupolar nucleus with a nuclear spin value of one, the...
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An ionic compound is stable because of the electrostatic attraction between its positive and negative ions. The lattice energy of a compound is a measure of the strength of this attraction. The lattice energy (ΔHlattice) of an ionic compound is defined as the energy required to separate one mole of the solid into its component gaseous ions. For the ionic solid sodium chloride, the lattice energy is the enthalpy change of the process:
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In the absence of an external magnetic field, nuclear spin states are degenerate and randomly oriented. When a magnetic field is applied, the spins begin to precess and orient themselves along (lower energy) or against (higher energy) the direction of the field. At equilibrium, a slight excess population of spins exists in the lower energy state. Because the direction of the magnetic field is fixed as the z-axis,  the precessing magnetic moments are randomly oriented around the z-axis.
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Nuclear quantum effects amplify autoionization-driven superionic behaviour in nanoconfined monolayer water.

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  • 1Yusuf Hamied Department of Chemistry, University of Cambridge Lensfield Road Cambridge CB2 1EW UK am452@cam.ac.uk v.kapil@ucl.ac.uk.

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Nuclear quantum effects drive a superionic phase transition in confined water monolayers at lower pressures than bulk water. This finding brings superionic behavior closer to experimental conditions for 2D material-water systems.

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Area of Science:

  • Physical Chemistry
  • Materials Science
  • Condensed Matter Physics

Background:

  • Nuclear quantum effects (NQEs) significantly impact water's properties, including autoionization.
  • Autoionization-driven phase transitions in bulk water typically require extreme pressures (tens to hundreds of GPa).
  • Understanding water behavior under confinement is crucial for nanotechnology and materials science.

Purpose of the Study:

  • To investigate the influence of nuclear quantum effects on water phase transitions under nanoconfinement.
  • To determine if NQEs can lower the pressure threshold for superionic phase transitions in confined water.
  • To assess the feasibility of observing these phenomena in experimental settings.

Main Methods:

  • Theoretical calculations were employed to model a monolayer of water confined within a uniform nanostructure.
  • Simulations focused on the role of nuclear quantum effects in driving phase transitions.
  • Comparison of transition pressures between confined water and bulk water was performed.

Main Results:

  • Nuclear quantum effects were found to induce a superionic phase transition in a water monolayer under milder conditions than in bulk water.
  • The calculated pressure regimes for this transition are significantly lower than those previously observed for bulk water.
  • This suggests that superionic behavior in confined water can be accessed at pressures relevant to current experimental techniques.

Conclusions:

  • Nanoconfinement, coupled with nuclear quantum effects, substantially lowers the pressure required for water's superionic phase transition.
  • These findings indicate that superionic water phases may be achievable in experiments involving 2D material-water encapsulation.
  • The study highlights the critical role of quantum effects and confinement in altering water's fundamental phase behavior.