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Classical theories of dielectric friction make two critical assumptions: (i) friction due to van der Waals (vdW) forces is described by hydrodynamic drag and is independent of the ionic charge and (ii) vdW and electrostatic forces are statistically independent. Both assumptions turn out to be incorrect when tested against simulations of anions and cations with varying charge magnitude dissolved in water. Both the vdW and electrostatic components of the force variance scale linearly with the ionic charge squared. The two components are strongly anticorrelated producing simple relations for the total force variance in terms of self-variances. The inverse diffusion constant scales linearly with the charge squared. Solvation asymmetry between cations and anions extends to linear transport coefficients.
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War and peace between electrostatic and van der Waals forces regulate translational and rotational diffusion
In the Stokes–Einstein picture, diffusion of a Brownian particle or a molecule in a liquid solvent is caused by unbalanced fluctuations of osmotic forces on different sides of the particle. When the particle carries a charge or a higher multipolar moment, this picture is amended by fluctuations of electrostatic forces producing dielectric friction. Dielectric friction slows down both the translational and rotational diffusion. While this picture is well established and is physically sound, standard theories grossly overestimate the magnitude of dielectric friction for small dipolar solutes and larger colloidal particles, such as proteins. Motivated by recent simulation studies, this Perspective discusses the interplay between osmotic (van der Waals) and electrostatic forces in promoting molecular and colloidal diffusion. Much can be learned about microscopic friction mechanisms from statistical and dynamical correlations between osmotic and electrostatic forces.
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- Award ID(s):
- 2154465
- PAR ID:
- 10399485
- Date Published:
- Journal Name:
- The Journal of Chemical Physics
- Volume:
- 157
- Issue:
- 8
- ISSN:
- 0021-9606
- Page Range / eLocation ID:
- 080901
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1063/5.0098506
