Jove
Visualize
Contact Us
JoVE
x logofacebook logolinkedin logoyoutube logo
ABOUT JoVE
OverviewLeadershipBlogJoVE Help Center
AUTHORS
Publishing ProcessEditorial BoardScope & PoliciesPeer ReviewFAQSubmit
LIBRARIANS
TestimonialsSubscriptionsAccessResourcesLibrary Advisory BoardFAQ
RESEARCH
JoVE JournalMethods CollectionsJoVE Encyclopedia of ExperimentsArchive
EDUCATION
JoVE CoreJoVE BusinessJoVE Science EducationJoVE Lab ManualFaculty Resource CenterFaculty Site
Terms & Conditions of Use
Privacy Policy
Policies

Related Experiment Videos

Alternative view of self-diffusion and shear viscosity.

Frank H Stillinger1, Pablo G Debenedetti

  • 1Department of Chemistry, Princeton University, Princeton, New Jersey 08544, USA.

The Journal of Physical Chemistry. B
|July 21, 2006
PubMed
Summary

Reformulating the self-diffusion constant (D) and shear viscosity (eta) expressions reveals how initial particle momentum influences displacement. Deeply supercooled liquids violate the Stokes-Einstein relation due to Markovian transitions affecting viscosity differently than diffusion.

Related Concept Videos

You might also read

Related Articles

Articles linked to this work by shared authors, journal, and citation graph.

Sort by
Same author

Energy landscape statistics and thermodynamics of a machine-learned model of water.

Proceedings of the National Academy of Sciences of the United States of America·2026
Same author

Tribute to Athanassios Z. Panagiotopoulos.

The journal of physical chemistry. B·2025
Same author

Machine learning in chemistry.

Proceedings of the National Academy of Sciences of the United States of America·2025
Same author

Computational investigation of water glasses using machine-learning potentials.

Proceedings of the National Academy of Sciences of the United States of America·2025
Same author

On the Possibility of Chiral Symmetry Breaking in Liquid Hydrogen Peroxide.

The journal of physical chemistry. B·2025
Same author

Anneke Levelt Sengers: An international authority in the thermodynamics of fluids and a passionate advocate for women in science.

Proceedings of the National Academy of Sciences of the United States of America·2024

Area of Science:

  • Physical Chemistry
  • Statistical Mechanics
  • Condensed Matter Physics

Background:

  • The Stokes-Einstein relation connects self-diffusion (D) and viscosity (eta) in liquids, stating D is proportional to T/eta.
  • Experimental studies show significant deviations from this relation in deeply supercooled liquids.
  • Understanding these deviations is crucial for comprehending liquid dynamics at low temperatures.

Purpose of the Study:

  • To reformulate expressions for the self-diffusion constant D(T,rho) and the inverse of shear viscosity 1/eta(T,rho).
  • To investigate the underlying mechanisms responsible for violations of the Stokes-Einstein relation in supercooled liquids.
  • To analyze the role of initial particle momentum and kinetic transitions in liquid dynamics.

Main Methods:

Related Experiment Videos

  • Reformulation of the velocity autocorrelation function for D(T,rho) using elementary transformations.
  • Derivation of an analogous expression for 1/eta(T,rho) employing collective flow variables.
  • Analysis of self-diffusion and viscous flow in terms of configuration space inherent structures and kinetic transitions between basins.

    • Main Results:

    • A reformulated expression for D(T,rho) highlights the influence of initial particle momentum on mean displacement.
    • An analogous expression for 1/eta(T,rho) was derived, linking viscosity to collective flow variables.
    • Analysis suggests that the increasing Markovian nature of interbasin transitions at low temperatures contributes to Stokes-Einstein violations.

    Conclusions:

    • Shear viscosity, unlike self-diffusion, intrinsically depends on successive correlated transitions, not just Markovian ones.
    • The differing dependence on transition dynamics explains the observed violations of the Stokes-Einstein relation in supercooled liquids.
    • This work provides a mechanistic insight into the breakdown of the Stokes-Einstein relation by dissecting the roles of inherent structures and kinetic transitions.