REAL

Calculation of the Intrinsic Solvation Free Energy Profile of an Ionic Penetrant Across a Liquid–Liquid Interface with Computer Simulations

Darvas, Mária and Jorge, Miguel and Cordeiro, M. Natalia D. S. and Jedlovszky, Pál (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 - CONDENSED MATTER MATERIALS SURFACES INTERFACES AND BIOPHYSICAL, 117 (50). pp. 16148-16156. ISSN 1520-6106

[img]
Preview
Text
jp_intrinsic_PMF_teljes_cikk.pdf

Download (1MB) | Preview

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.

Item Type: Article
Subjects: Q Science / természettudomány > QD Chemistry / kémia > QD01 Analytical chemistry / analitikai kémia
SWORD Depositor: MTMT SWORD
Depositing User: MTMT SWORD
Date Deposited: 09 Jan 2014 14:45
Last Modified: 09 Jan 2014 14:45
URI: http://real.mtak.hu/id/eprint/8526

Actions (login required)

View Item View Item