Ion Pair Structures in Aqueous KSCN Solution: Classical and Quantum Mechanical/Molecular Mechanical Molecular Dynamics Simulation Study

Manik Kumer Ghosh, Jun Ho Choi, Cheol Ho Choi, Minhaeng Cho

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

Ion pair formation and dissociation are fundamental processes in electrolyte solutions so that understanding thermodynamic stabilities and dynamic aspects of ion pairs is of great importance. The structures of various ion pair states are here studied by carrying out classical and quantum mechanical/molecular mechanical (QM/MM) molecular dynamics (MD) simulations of aqueous KSCN solutions. A few different solvent potential models are considered and the resulting ion pair structures are directly compared. In particular, when KSCN is treated quantum mechanically and effective fragment potential (EFP) model for water is used, we found two stable forms of ion pairs that can be considered as contact ion pair (CIP) and solvent separated ion pair (SSIP), where the interionic distances between K<sup>+</sup> and SCN<sup>-</sup> are found to be 4.0 and 5.5 Å, respectively. QM/EFP-MD further indicates that the nitrogen side of SCN<sup>-</sup> is preferentially interacting with K<sup>+</sup> in CIP. However, the corresponding CIP appears at 3.0 Å interionic distance in fully classical MD simulation at a higher KSCN concentration. Nonetheless, both QM/EFP and classical MD simulation results show that the CIP state appears to be more stable than SSIP. From the site-site radial distribution functions (RDF) calculated from the QM/MM and classical MD trajectories, detailed ion pair structures and surrounding solvent configurations are further elucidated.

Original languageEnglish
Pages (from-to)944-949
Number of pages6
JournalBulletin of the Korean Chemical Society
Volume36
Issue number3
DOIs
Publication statusPublished - 2015 Mar 1

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Molecular dynamics
Ions
Computer simulation
potassium thiocyanate
Electrolytes
Distribution functions
Thermodynamic stability
Nitrogen
Trajectories
Water

Keywords

  • Hofmeister series
  • Ion pairing
  • KSCN
  • Molecular dynamics
  • QM/MM-MD

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Ion Pair Structures in Aqueous KSCN Solution : Classical and Quantum Mechanical/Molecular Mechanical Molecular Dynamics Simulation Study. / Ghosh, Manik Kumer; Choi, Jun Ho; Choi, Cheol Ho; Cho, Minhaeng.

In: Bulletin of the Korean Chemical Society, Vol. 36, No. 3, 01.03.2015, p. 944-949.

Research output: Contribution to journalArticle

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