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

Darvas, Maria and Jorge, Miguel and D. S. Cordeiro, M. Natalia and Kantorovich, Sofia S and Sega, Marcello and Jedlovszky, Pal (2013) Calculation of the intrinsic solvation free energy profile of an ionic penetrant across a liquid/liquid interface with computer simulations. Journal of Physical Chemistry B, 117 (50). 16148–16156. ISSN 1520-6106 (https://doi.org/10.1021/jp404699t)

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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.

ORCID iDs

Darvas, Maria, Jorge, Miguel ORCID logoORCID: https://orcid.org/0000-0003-3009-4725, D. S. Cordeiro, M. Natalia, Kantorovich, Sofia S, Sega, Marcello and Jedlovszky, Pal;
  • Item type:Article
    ID code:48044
    Dates:
    Date
    Event
    2013
    Published
    31 October 2013
    Published Online
    Notes:This document is the unedited Author’s version of a Submitted Work that was subsequently accepted for publication in The Journal of Physical Chemistry B, copyright © American Chemical Society after peer review. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/jp404699t.
    Subjects:Technology > Chemical engineering
    Science > Chemistry
    Science > Physics
    Department:Faculty of Engineering > Chemical and Process Engineering
    Depositing user: Pure Administrator
    Date deposited:13 May 2014 10:56
    Last modified:18 Nov 2024 01:07
    Related URLs:
    URI:https://strathprints.strath.ac.uk/id/eprint/48044
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