Electroosmotic Flow in Nanoscale Parallel-plate Channels: Molecular Simulation Study and Comparison with Classical Poisson–Boltzmann Theory

Abstract

Molecular dynamics simulations have been carried out for simple electrolyte systems to study the electrokinetically driven osmotic flow in parallel-plate channels of widths ∼10–120 nm. The results are compared with the classical theory predictions based on the solution to the Poisson–Boltzmann equation. We find that despite some of the limitations in the Poisson–Boltzmann equation, such as assumption of the Boltzmann distribution for the ions, the classical theory captures the general trend of the variations of the osmotic flow with channel width, as characterized by the mobility of the fluid in channels between ∼10 and 120 nm at moderate to low ion concentration. At moderate concentration (corresponding to relatively low surface potential), the classical theory is almost quantitative. The theory and simulation show more disagreement at low concentration, primarily caused by the high surface potential where the assumption of Boltzmann distribution becomes inaccurate. We discuss the limitations of the Poisson–Boltzmann equation as applied to the nanoscale channels.

Keywords:

• Electroosmotic flow
• Parallel-plate channels
• Molecular dynamics simulations
• Poisson–Boltzmann theory

Acknowledgements

The authors acknowledge many helpful discussions with Mike Ramsey and his group. This work is supported in part by the NSF at UT under contract BES-0103140, by DARPA at ORNL, and by the Chemical Sciences Division of DOE at ORNL. ORNL is operated for the U.S. DOE by UT-Battelle, LLC, under contract DE-AC05-00OR22725.