Structural and energetic effects of truncating long ranged interactions in ionic and polar fluids

Charles L. Brooks, Bernard Pettitt, Martin Karplus

Research output: Contribution to journalArticle

247 Citations (Scopus)

Abstract

The effects of Coulomb potential truncation schemes used in computer simulations of ionic and polar fluids are examined by use of integral equation techniques. A renormalized HNC type equation capable of describing both ionic and polar molecular fluids with truncated interactions is derived and applied to several model systems of interest. Good agreement is found between the integral equation results and Monte Carlo simulations of the same potential for dilute solutions of ions in a dielectric continuum. Very large effects on the distribution functions result from truncation of the electrostatic interaction in dilute systems. Even in comparatively dense systems, unrealistic pair correlations near the cutoff distance result from some of the proposed truncation schemes. The effect of Coulomb potential truncation for a molecular model of pure water is also studied. Significant errors appear in the second neighbor region for commonly used truncation schemes; a simple switching function that zeros the potential and its first derivative yields results closest to the Coulomb potential without truncation.

Original languageEnglish (US)
Pages (from-to)5897-5908
Number of pages12
JournalThe Journal of Chemical Physics
Volume83
Issue number11
StatePublished - 1985
Externally publishedYes

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Integral equations
Switching functions
Fluids
fluids
Coulomb potential
Coulomb interactions
approximation
Distribution functions
interactions
Ions
Derivatives
integral equations
Water
Computer simulation
cut-off
computerized simulation
distribution functions
electrostatics
continuums
water

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

Structural and energetic effects of truncating long ranged interactions in ionic and polar fluids. / Brooks, Charles L.; Pettitt, Bernard; Karplus, Martin.

In: The Journal of Chemical Physics, Vol. 83, No. 11, 1985, p. 5897-5908.

Research output: Contribution to journalArticle

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