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

• Tipo: Artigo em Revista Científica Internacional
• Data: 2013

Autores

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

Revista

Título: Journal of Physical Chemistry B

Vol. 117

Páginas: 16148-16156

ISSN: 1520-6106

Editora: American Chemical Society

Indexação

ISI Web of Knowledge - 29 Citações

Scopus - 29 Citações

Classificação Científica

FOS: Ciências exactas e naturais > Química

Outras Informações

ID Authenticus: 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.

Idioma: Inglês

Tipo (Avaliação Docente): Científica