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Long-time dynamics of Rouse-Zimm polymers in dilute solutions with hydrodynamic memory.

V Lisy1, J Tothova, A V Zatovsky

  • 1Institute of Physics, P.J. Safarik University, Jesenna 5, 04154 Kosice, Slovakia. lisy@upjs.sk

The Journal of Chemical Physics
|November 20, 2004
PubMed
Summary

This study reveals that polymer dynamics in solution differ from the Rouse-Zimm theory due to fluid inertia. These findings, including altered polymer diffusion, may be observable in dynamic scattering experiments.

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Area of Science:

  • Polymer Physics
  • Fluid Dynamics
  • Statistical Mechanics

Background:

  • The Rouse-Zimm (RZ) theory describes flexible polymer dynamics in dilute solutions.
  • The RZ model assumes Stokes drag and neglects fluid inertia and hydrodynamic memory effects.

Purpose of the Study:

  • To investigate the impact of hydrodynamic memory and fluid inertia on flexible polymer dynamics.
  • To develop a generalized Rouse-Zimm model incorporating these effects.

Main Methods:

  • The study employs a generalized Rouse-Zimm equation derived from nonstationary Navier-Stokes equations for solvent motion.
  • Boussinesq friction is used instead of Stokes force for monomer interactions.
  • The generalized equation is solved using approximate methods, including preaveraging of the Oseen tensor.

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Main Results:

  • Polymer dynamics and time correlation functions deviate significantly from the standard RZ model.
  • Mean-square displacement (MSD) shows a t^2 dependence at short times and additional t contributions at long times.
  • Internal normal mode relaxation exhibits long-time tails (t^-3/2 or t^-5/2) instead of exponential decay.

Conclusions:

  • The inclusion of hydrodynamic memory and fluid inertia leads to distinct polymer dynamics, including slower diffusion.
  • These theoretical predictions, such as altered MSD and relaxation behavior, warrant experimental verification through dynamic scattering.
  • The generalized model offers a more comprehensive description of polymer behavior in solution under specific conditions.