Solvent electronic polarization effects on Na+-Na+ and Cl--Cl- pair associations in aqueous solution

Cheol Ho Choi, Suyong Re, Mohammad H.O. Rashid, Hui Li, Michael Feig, Yuji Sugita

Research output: Contribution to journalArticle

16 Citations (Scopus)

Abstract

The formation of like-ion pairs, Na+-Na+ and Cl --Cl-, in aqueous solution was studied by high-level ab initio methods, classical molecular dynamics (MD), QM/TIP5P, and QM/EFP MD (quantum mechanics/effective fragment potential molecular dynamics). Ab initio calculations on model clusters revealed that the Na+(H 2O)nNa+ (n = 2-4) clusters were significantly more stabilized by bridged waters than the corresponding Cl-(H 2O)nCl- clusters. QM/EFP MD simulations in solution also predicted a clear local minimum near 3.6 Å only for the Na+-Na+ pair, suggesting that Na+-Na + pairs may be more likely to form than Cl--Cl- pairs in solution. Analysis of the hydration structures further showed that two-water bridged Na+-Na+ pairs were dominant at the local minimum. The preferred formation of Na+ like-ion pairs in solution appeared to come from significant short-range effects, in particular, charge delocalization (polarization) between the bridged oxygen p and the vacant valence Na+ orbitals.

Original languageEnglish (US)
Pages (from-to)9273-9279
Number of pages7
JournalJournal of Physical Chemistry B
Volume117
Issue number31
DOIs
StatePublished - Aug 8 2013

Fingerprint

Molecular dynamics
Polarization
molecular dynamics
aqueous solutions
polarization
electronics
Ions
Water
Quantum theory
Hydration
water
hydration
quantum mechanics
ions
fragments
Oxygen
valence
orbitals
Hydrogen
Computer simulation

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry

Cite this

Solvent electronic polarization effects on Na+-Na+ and Cl--Cl- pair associations in aqueous solution. / Choi, Cheol Ho; Re, Suyong; Rashid, Mohammad H.O.; Li, Hui; Feig, Michael; Sugita, Yuji.

In: Journal of Physical Chemistry B, Vol. 117, No. 31, 08.08.2013, p. 9273-9279.

Research output: Contribution to journalArticle

Choi, Cheol Ho ; Re, Suyong ; Rashid, Mohammad H.O. ; Li, Hui ; Feig, Michael ; Sugita, Yuji. / Solvent electronic polarization effects on Na+-Na+ and Cl--Cl- pair associations in aqueous solution. In: Journal of Physical Chemistry B. 2013 ; Vol. 117, No. 31. pp. 9273-9279.
@article{7c374a4448c644d7aaab6c4765c9adfc,
title = "Solvent electronic polarization effects on Na+-Na+ and Cl--Cl- pair associations in aqueous solution",
abstract = "The formation of like-ion pairs, Na+-Na+ and Cl --Cl-, in aqueous solution was studied by high-level ab initio methods, classical molecular dynamics (MD), QM/TIP5P, and QM/EFP MD (quantum mechanics/effective fragment potential molecular dynamics). Ab initio calculations on model clusters revealed that the Na+(H 2O)nNa+ (n = 2-4) clusters were significantly more stabilized by bridged waters than the corresponding Cl-(H 2O)nCl- clusters. QM/EFP MD simulations in solution also predicted a clear local minimum near 3.6 {\AA} only for the Na+-Na+ pair, suggesting that Na+-Na + pairs may be more likely to form than Cl--Cl- pairs in solution. Analysis of the hydration structures further showed that two-water bridged Na+-Na+ pairs were dominant at the local minimum. The preferred formation of Na+ like-ion pairs in solution appeared to come from significant short-range effects, in particular, charge delocalization (polarization) between the bridged oxygen p and the vacant valence Na+ orbitals.",
author = "Choi, {Cheol Ho} and Suyong Re and Rashid, {Mohammad H.O.} and Hui Li and Michael Feig and Yuji Sugita",
year = "2013",
month = "8",
day = "8",
doi = "10.1021/jp4049346",
language = "English (US)",
volume = "117",
pages = "9273--9279",
journal = "Journal of Physical Chemistry B Materials",
issn = "1520-6106",
publisher = "American Chemical Society",
number = "31",

}

TY - JOUR

T1 - Solvent electronic polarization effects on Na+-Na+ and Cl--Cl- pair associations in aqueous solution

AU - Choi, Cheol Ho

AU - Re, Suyong

AU - Rashid, Mohammad H.O.

AU - Li, Hui

AU - Feig, Michael

AU - Sugita, Yuji

PY - 2013/8/8

Y1 - 2013/8/8

N2 - The formation of like-ion pairs, Na+-Na+ and Cl --Cl-, in aqueous solution was studied by high-level ab initio methods, classical molecular dynamics (MD), QM/TIP5P, and QM/EFP MD (quantum mechanics/effective fragment potential molecular dynamics). Ab initio calculations on model clusters revealed that the Na+(H 2O)nNa+ (n = 2-4) clusters were significantly more stabilized by bridged waters than the corresponding Cl-(H 2O)nCl- clusters. QM/EFP MD simulations in solution also predicted a clear local minimum near 3.6 Å only for the Na+-Na+ pair, suggesting that Na+-Na + pairs may be more likely to form than Cl--Cl- pairs in solution. Analysis of the hydration structures further showed that two-water bridged Na+-Na+ pairs were dominant at the local minimum. The preferred formation of Na+ like-ion pairs in solution appeared to come from significant short-range effects, in particular, charge delocalization (polarization) between the bridged oxygen p and the vacant valence Na+ orbitals.

AB - The formation of like-ion pairs, Na+-Na+ and Cl --Cl-, in aqueous solution was studied by high-level ab initio methods, classical molecular dynamics (MD), QM/TIP5P, and QM/EFP MD (quantum mechanics/effective fragment potential molecular dynamics). Ab initio calculations on model clusters revealed that the Na+(H 2O)nNa+ (n = 2-4) clusters were significantly more stabilized by bridged waters than the corresponding Cl-(H 2O)nCl- clusters. QM/EFP MD simulations in solution also predicted a clear local minimum near 3.6 Å only for the Na+-Na+ pair, suggesting that Na+-Na + pairs may be more likely to form than Cl--Cl- pairs in solution. Analysis of the hydration structures further showed that two-water bridged Na+-Na+ pairs were dominant at the local minimum. The preferred formation of Na+ like-ion pairs in solution appeared to come from significant short-range effects, in particular, charge delocalization (polarization) between the bridged oxygen p and the vacant valence Na+ orbitals.

UR - http://www.scopus.com/inward/record.url?scp=84881396365&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84881396365&partnerID=8YFLogxK

U2 - 10.1021/jp4049346

DO - 10.1021/jp4049346

M3 - Article

VL - 117

SP - 9273

EP - 9279

JO - Journal of Physical Chemistry B Materials

JF - Journal of Physical Chemistry B Materials

SN - 1520-6106

IS - 31

ER -