A systematic molecular simulation study of ionic liquid surfaces using intrinsic analysis methods

Gyoergy Hantal, Iuliia Voroshylova, M. Natalia D. S. Cordeiro, Miguel Jorge

Research output: Contribution to journalArticle

46 Citations (Scopus)

Abstract

In this paper, we apply novel intrinsic analysis methods, coupled with bivariate orientation analysis, to obtain a detailed picture of the molecular-level structure of ionic liquid surfaces. We observe pronounced layering at the interface, alternating non-polar with ionic regions. The outermost regions of the surface are populated by alkyl chains, which are followed by a dense and tightly packed layer formed of oppositely charged ionic moieties. We then systematically change the cation chain length, the anion size, the temperature and the molecular model, to examine the effect of each of these parameters on the interfacial structure. Increasing the cation chain length promotes orientations in which the chain is pointing into the vapor, thus increasing the coverage of the surface with alkyl groups. Larger anions promote a disruption of the dense ionic layer, increasing the orientational freedom of cations and increasing the amount of free space. The temperature had a relatively small effect on the surface structure, while the effect of the choice of molecular model was clearly significant, particularly on the orientational preferences at the interface. Our study demonstrates the usefulness of molecular simulation methods in the design of ionic liquids to suit particular applications.

LanguageEnglish
Pages5200-5213
Number of pages14
JournalPhysical Chemistry Chemical Physics
Volume14
Issue number15
Early online date2 Mar 2012
DOIs
Publication statusPublished - 2012

Fingerprint

Ionic Liquids
liquid surfaces
Cations
Chain length
Anions
cations
simulation
anions
Surface structure
Vapors
Temperature
vapors
temperature
liquids

Keywords

  • molecular simulation
  • intrinsic analysis methods
  • ionic liquid surfaces
  • study
  • systematic analytical-based generalised algorithm

Cite this

Hantal, Gyoergy ; Voroshylova, Iuliia ; Cordeiro, M. Natalia D. S. ; Jorge, Miguel. / A systematic molecular simulation study of ionic liquid surfaces using intrinsic analysis methods. In: Physical Chemistry Chemical Physics. 2012 ; Vol. 14, No. 15. pp. 5200-5213.
@article{f68e0e32197e45a2946de3d8470a6ee2,
title = "A systematic molecular simulation study of ionic liquid surfaces using intrinsic analysis methods",
abstract = "In this paper, we apply novel intrinsic analysis methods, coupled with bivariate orientation analysis, to obtain a detailed picture of the molecular-level structure of ionic liquid surfaces. We observe pronounced layering at the interface, alternating non-polar with ionic regions. The outermost regions of the surface are populated by alkyl chains, which are followed by a dense and tightly packed layer formed of oppositely charged ionic moieties. We then systematically change the cation chain length, the anion size, the temperature and the molecular model, to examine the effect of each of these parameters on the interfacial structure. Increasing the cation chain length promotes orientations in which the chain is pointing into the vapor, thus increasing the coverage of the surface with alkyl groups. Larger anions promote a disruption of the dense ionic layer, increasing the orientational freedom of cations and increasing the amount of free space. The temperature had a relatively small effect on the surface structure, while the effect of the choice of molecular model was clearly significant, particularly on the orientational preferences at the interface. Our study demonstrates the usefulness of molecular simulation methods in the design of ionic liquids to suit particular applications.",
keywords = "molecular simulation, intrinsic analysis methods , ionic liquid surfaces , study , systematic analytical-based generalised algorithm",
author = "Gyoergy Hantal and Iuliia Voroshylova and Cordeiro, {M. Natalia D. S.} and Miguel Jorge",
year = "2012",
doi = "10.1039/c2cp23967a",
language = "English",
volume = "14",
pages = "5200--5213",
journal = "Physical Chemistry Chemical Physics",
issn = "1463-9076",
number = "15",

}

A systematic molecular simulation study of ionic liquid surfaces using intrinsic analysis methods. / Hantal, Gyoergy; Voroshylova, Iuliia; Cordeiro, M. Natalia D. S.; Jorge, Miguel.

In: Physical Chemistry Chemical Physics, Vol. 14, No. 15, 2012, p. 5200-5213.

Research output: Contribution to journalArticle

TY - JOUR

T1 - A systematic molecular simulation study of ionic liquid surfaces using intrinsic analysis methods

AU - Hantal, Gyoergy

AU - Voroshylova, Iuliia

AU - Cordeiro, M. Natalia D. S.

AU - Jorge, Miguel

PY - 2012

Y1 - 2012

N2 - In this paper, we apply novel intrinsic analysis methods, coupled with bivariate orientation analysis, to obtain a detailed picture of the molecular-level structure of ionic liquid surfaces. We observe pronounced layering at the interface, alternating non-polar with ionic regions. The outermost regions of the surface are populated by alkyl chains, which are followed by a dense and tightly packed layer formed of oppositely charged ionic moieties. We then systematically change the cation chain length, the anion size, the temperature and the molecular model, to examine the effect of each of these parameters on the interfacial structure. Increasing the cation chain length promotes orientations in which the chain is pointing into the vapor, thus increasing the coverage of the surface with alkyl groups. Larger anions promote a disruption of the dense ionic layer, increasing the orientational freedom of cations and increasing the amount of free space. The temperature had a relatively small effect on the surface structure, while the effect of the choice of molecular model was clearly significant, particularly on the orientational preferences at the interface. Our study demonstrates the usefulness of molecular simulation methods in the design of ionic liquids to suit particular applications.

AB - In this paper, we apply novel intrinsic analysis methods, coupled with bivariate orientation analysis, to obtain a detailed picture of the molecular-level structure of ionic liquid surfaces. We observe pronounced layering at the interface, alternating non-polar with ionic regions. The outermost regions of the surface are populated by alkyl chains, which are followed by a dense and tightly packed layer formed of oppositely charged ionic moieties. We then systematically change the cation chain length, the anion size, the temperature and the molecular model, to examine the effect of each of these parameters on the interfacial structure. Increasing the cation chain length promotes orientations in which the chain is pointing into the vapor, thus increasing the coverage of the surface with alkyl groups. Larger anions promote a disruption of the dense ionic layer, increasing the orientational freedom of cations and increasing the amount of free space. The temperature had a relatively small effect on the surface structure, while the effect of the choice of molecular model was clearly significant, particularly on the orientational preferences at the interface. Our study demonstrates the usefulness of molecular simulation methods in the design of ionic liquids to suit particular applications.

KW - molecular simulation

KW - intrinsic analysis methods

KW - ionic liquid surfaces

KW - study

KW - systematic analytical-based generalised algorithm

UR - http://pubs.rsc.org/en/journals/journalissues/cp

U2 - 10.1039/c2cp23967a

DO - 10.1039/c2cp23967a

M3 - Article

VL - 14

SP - 5200

EP - 5213

JO - Physical Chemistry Chemical Physics

T2 - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

SN - 1463-9076

IS - 15

ER -