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Enhanced Molecular Diffusivity through Destructive Interference between Electrostatic and Osmotic Forces.

Tuhin Samanta1, Setare Mostajabi Sarhangi1, Dmitry V Matyushov1

  • 1School of Molecular Sciences and Department of Physics, Arizona State University, P. O. Box 871504, Tempe, Arizona 85287-1504, United States.

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This summary is machine-generated.

Asymmetric molecular charge creates opposing electrostatic and van der Waals forces, leading to faster particle diffusion in water due to a frozen hydration layer. This effect impacts smaller particles more than proteins.

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Area of Science:

  • Physical Chemistry
  • Colloid Science
  • Molecular Dynamics

Background:

  • Particle diffusion in liquids is typically described by theories of dielectric friction.
  • The role of correlated force fluctuations and hydration layers in diffusion is not fully understood.

Purpose of the Study:

  • To investigate the impact of asymmetric molecular charge on particle diffusion in water.
  • To explain the observed speedup in translational diffusion compared to conventional models.

Main Methods:

  • Molecular dynamics simulations were used to model a diffusing tagged particle.
  • Analysis of electrostatic and van der Waals (vdW) force fluctuations.
  • Calculation of the effective dielectric constant of interfacial water.

Main Results:

  • Asymmetric charge distribution leads to correlated electrostatic and vdW forces that destructively interfere.
  • A structurally frozen hydration layer is formed, causing a significant speedup in translational diffusion.
  • Protein diffusion is largely unaffected by charge mutations, unlike smaller particles.

Conclusions:

  • The interplay between electrostatic and vdW forces, mediated by a frozen hydration layer, is crucial for understanding particle diffusion.
  • Dielectric calculations necessitate a low effective dielectric constant (≃5) for interfacial water to align with simulation findings.