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Updated: May 12, 2026

The Preparation of Electrohydrodynamic Bridges from Polar Dielectric Liquids
10:03

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Published on: September 30, 2014

Are polar liquids less simple?

D Fragiadakis1, C M Roland

  • 1Naval Research Laboratory, Chemistry Division, Code 6120, Washington, DC 20375-5342, USA.

The Journal of Chemical Physics
|April 6, 2013
PubMed
Summary
This summary is machine-generated.

Simple liquids show strong correlations between energy and virial fluctuations, predicting dynamic properties. Polar and hydrogen-bonded liquids deviate, with deviations linked to intermolecular potential, not just bonding or polarity.

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Area of Science:

  • Condensed matter physics
  • Physical chemistry
  • Computational materials science

Background:

  • A strong correlation exists between equilibrium fluctuations of potential energy (U) and virial (W) in liquids.
  • This correlation is linked to dynamic properties like density scaling and isochronal superpositioning.

Purpose of the Study:

  • To investigate the connection between U-W correlation and dynamic properties in liquids.
  • To use molecular dynamics simulations on methanol and its variations to test this connection.

Main Methods:

  • Molecular dynamics simulations were performed on methanol, a methanol variant lacking hydrogen bonds, and a variant lacking a dipole moment.
  • The study analyzed the correlation between potential energy (U) and virial (W) fluctuations under isochoric conditions.

Main Results:

  • Simple van der Waals liquids exhibit strong U-W correlations and expected dynamic behavior.
  • Polar liquids show weaker U-W correlations, but this does not negatively impact density scaling or isochronal superpositioning.
  • Hydrogen-bonded liquids display neither strong U-W correlation nor adherence to dynamic properties, attributed to deviations from inverse power-law potentials.

Conclusions:

  • The breakdown of the U-W correlation-dynamics link in polar liquids is due to the constancy of the proportionality constant, not just the correlation strength.
  • Deviations in hydrogen-bonded liquids are primarily caused by the intermolecular potential's deviation from an inverse power law.
  • Only liquids with strictly inverse power-law interactions perfectly exhibit these dynamic properties across all thermodynamic conditions.