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

• Type: Article in International Scientific Journal
• Date: 2013

Authors

Maria Darvas (Author) Other; Miguel Jorge (Author) Other; M Natalia D S Cordeiro (Author) FCUP; Sofia S Kantorovich (Author) Other; Marcello Sega (Author) Other; Pal Jedlovszky (Author) Other

Journal

Title: Journal of Physical Chemistry B

Vol. 117

Pages: 16148-16156

ISSN: 1520-6106

Publisher: American Chemical Society

Indexing

ISI Web of Knowledge - 29 Citations

Scopus - 29 Citations

Scientific classification

FOS: Natural sciences > Chemical sciences

Other information

Authenticus ID: P-008-K5W

DOI: 10.1021/jp404699t

Abstract (EN): 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.

Language: English

Type (Professor's evaluation): Scientific