A theoretical study of like ion pairs in solution

Liem X. Dang, Bernard Pettitt

Research output: Contribution to journalArticle

102 Citations (Scopus)

Abstract

Theoretical studies of ionic distributions in aqueous solutions have been carried out. The spatial pair distribution in ions in solution and the distribution of water near pairs of ions have been computed. Influences of solvent structure on ion pairing and the structural mechanisms of the pairing (or unpairing) process are investigated. We present a detailed picture of ionic distributions in solution which are compared with existing experimental structural studies such as those produced by neutron diffraction difference measurements and NMR experiments. The results of molecular dynamics simulations on the free energy of association for like-charged ions in water are presented. The influence of the solvent on the free energy surfaces (potentials of mean force) of Cl-Cl- and Na+Na+ is determined by using a dynamic trajectory in conjunction with a non-Boltzmann sampling approach for the interionic degree of freedom. The potential of mean force for the anionic pair C1-C1- in water reveals a minimum near ion contact due to the presence of several bridging water molecules, whereas the cationic Na+Na+ potential of mean force is found to be essentially repulsive. The results are in general agreement with site-site integral equation results on the same models.

Original languageEnglish
Pages (from-to)4303-4308
Number of pages6
JournalJournal of Physical Chemistry®
Volume94
Issue number10
StatePublished - 1990
Externally publishedYes

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Ions
Water
ions
water
Free energy
free energy
Surface potential
Neutron diffraction
Spatial distribution
Integral equations
neutron diffraction
Molecular dynamics
integral equations
degrees of freedom
sampling
Trajectories
Nuclear magnetic resonance
Association reactions
trajectories
molecular dynamics

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

A theoretical study of like ion pairs in solution. / Dang, Liem X.; Pettitt, Bernard.

In: Journal of Physical Chemistry®, Vol. 94, No. 10, 1990, p. 4303-4308.

Research output: Contribution to journalArticle

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