Ionic mobility driven by correlated van der Waals and electrostatic forces

Tuhin Samanta, Dmitry V. Matyushov

Research output: Contribution to journalArticlepeer-review

Abstract

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.

Original languageEnglish (US)
Article number204501
JournalJournal of Chemical Physics
Volume156
Issue number20
DOIs
StatePublished - May 28 2022

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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