Calculation of the intrinsic solvation free energy profile of an ionic penetrant across a liquid/liquid interface with computer simulations

Maria Darvas, Miguel Jorge, M. Natalia D. S. Cordeiro, Sofia S Kantorovich, Marcello Sega, Pal Jedlovszky

Research output: Contribution to journalArticle

18 Citations (Scopus)

Abstract

We introduce the novel concept of an intrinsic free energy profile, allowing one to remove the artificial smearing caused by thermal capillary waves, which renders difficulties for the calculation of free energy profiles across fluid interfaces in computer simulations. We apply this concept to the problem of a chloride ion crossing the interface between water and 1,2-dichloroethane and show that the present approach is able to reveal several important features of the free energy profile which are not detected with the usual, nonintrinsic calculations. Thus, in contrast to the nonintrinsic profile, a free energy barrier is found at the aqueous side of the (intrinsic) interface, which is attributed to the formation of a water “finger” the ion pulls with itself upon approaching the organic phase. Further, by the presence of a nonsampled region, the intrinsic free energy profile clearly indicates the coextraction of the first hydration shell water molecules of the ion when entering the organic phase.
LanguageEnglish
Pages16148–16156
Number of pages9
JournalJournal of Physical Chemistry B
Volume117
Issue number50
Early online date31 Oct 2013
DOIs
Publication statusPublished - 2013

Fingerprint

penetrants
liquid-liquid interfaces
Solvation
Free energy
solvation
computerized simulation
free energy
Computer simulation
Liquids
profiles
Ions
Water
water
ions
capillary waves
Energy barriers
Hydration
hydration
Chlorides
chlorides

Keywords

  • calculation
  • instrinsic
  • solvation free
  • energy profile
  • ionic penetrant
  • liquid-liquid interface
  • computer simulations

Cite this

Darvas, Maria ; Jorge, Miguel ; D. S. Cordeiro, M. Natalia ; Kantorovich, Sofia S ; Sega, Marcello ; Jedlovszky, Pal. / Calculation of the intrinsic solvation free energy profile of an ionic penetrant across a liquid/liquid interface with computer simulations. In: Journal of Physical Chemistry B. 2013 ; Vol. 117, No. 50. pp. 16148–16156.
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abstract = "We introduce the novel concept of an intrinsic free energy profile, allowing one to remove the artificial smearing caused by thermal capillary waves, which renders difficulties for the calculation of free energy profiles across fluid interfaces in computer simulations. We apply this concept to the problem of a chloride ion crossing the interface between water and 1,2-dichloroethane and show that the present approach is able to reveal several important features of the free energy profile which are not detected with the usual, nonintrinsic calculations. Thus, in contrast to the nonintrinsic profile, a free energy barrier is found at the aqueous side of the (intrinsic) interface, which is attributed to the formation of a water “finger” the ion pulls with itself upon approaching the organic phase. Further, by the presence of a nonsampled region, the intrinsic free energy profile clearly indicates the coextraction of the first hydration shell water molecules of the ion when entering the organic phase.",
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Calculation of the intrinsic solvation free energy profile of an ionic penetrant across a liquid/liquid interface with computer simulations. / Darvas, Maria; Jorge, Miguel; D. S. Cordeiro, M. Natalia; Kantorovich, Sofia S; Sega, Marcello; Jedlovszky, Pal.

In: Journal of Physical Chemistry B, Vol. 117, No. 50, 2013, p. 16148–16156.

Research output: Contribution to journalArticle

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AU - Sega, Marcello

AU - Jedlovszky, Pal

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