The intrinsic structure of the interface of partially miscible fluids: an application to ionic liquids

Gyoergy Hantal, Marcello Sega, Sofia S Kantorovich, Christian Schröder, Miguel Jorge

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

We investigate by means of Molecular Dynamics simulations how the intrinsic sur- face structure of liquid/liquid interfaces involving ionic liquids depends on the opposite phase of varying polarity. We study 1-n-butyl-3-methylimidazolium hexa uorophos- phate (BMIM PF 6 ) and 1-n-butyl-3-methylimidazolium bis(tri uoromethylsulfonyl)imid (BMIM NTf 2 ). The opposite phase is either cyclohexane or water, but as a reference, IL { vacuum interfaces are also studied. We combine a distance-based cluster search algorithm with the ITIM intrinsic analyzing method to separate liquid phases showing non-negligible mutual miscibility and to identify atoms residing at the instantaneous surface. In contrast to the well structured surface of IL { vacuum systems, at liq- uid/liquid interfaces of ILs density correlations, ionic associations and orientational preferences are all weakened, this eect being much more pronounced when the other species is water. In such systems we observe a drastic reduction in the presence of the cation at the surface and an increase of appearance of polar moieties (of both the cations and anions) leading to decreased apolar character of the interface. Furthermore, cations are mostly found to turn with their butyl chains toward the bulk while having their methyl groups sticking towards water. Anion-cation associations are reduced and partially replaced by water-anion and rarely also water-cation associations.
LanguageEnglish
Pages28448–28461
Number of pages14
JournalJournal of Physical Chemistry C
Volume119
Issue number51
DOIs
Publication statusPublished - 23 Nov 2015

Fingerprint

Ionic Liquids
Ionic liquids
Cations
Positive ions
cations
Fluids
Water
fluids
Liquids
Anions
liquids
liquid-liquid interfaces
Negative ions
water
anions
Vacuum
vacuum systems
Cyclohexane
cyclohexane
Molecular dynamics

Keywords

  • molecular dynamics
  • surface structure
  • ionic liquids

Cite this

Hantal, Gyoergy ; Sega, Marcello ; Kantorovich, Sofia S ; Schröder, Christian ; Jorge, Miguel. / The intrinsic structure of the interface of partially miscible fluids : an application to ionic liquids. In: Journal of Physical Chemistry C. 2015 ; Vol. 119, No. 51. pp. 28448–28461.
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The intrinsic structure of the interface of partially miscible fluids : an application to ionic liquids. / Hantal, Gyoergy; Sega, Marcello; Kantorovich, Sofia S; Schröder, Christian; Jorge, Miguel.

In: Journal of Physical Chemistry C, Vol. 119, No. 51, 23.11.2015, p. 28448–28461.

Research output: Contribution to journalArticle

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