Surface behaviour of 1-alkyl-3-methylimidazolium ionic liquids at the air-water interface
Molecular dynamics simulations snapshots and electron density determined by X-ray reflectivity on layers of C20mimNTf2 ionic liquid at the air water interface undergoing a monolayer to trilayer transition with increase of surface density. [Display omitted] •1-alkyl-3-methylimidazolium ionic liquids...
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Published in | Journal of molecular liquids Vol. 370; p. 121028 |
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Main Authors | , , , , , , , , , |
Format | Journal Article |
Language | English |
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Elsevier B.V
15.01.2023
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Abstract | Molecular dynamics simulations snapshots and electron density determined by X-ray reflectivity on layers of C20mimNTf2 ionic liquid at the air water interface undergoing a monolayer to trilayer transition with increase of surface density.
[Display omitted]
•1-alkyl-3-methylimidazolium ionic liquids with chain longer than 16 carbons and with NTF2 cation forms Langmuir monolayers.•For [C20mim][NTf2], X-ray diffraction reveal a transition from an expanded monolayer to a trilayer organized structure.•The monolayer to trilayer transition was reproduced by atomistic molecular dynamics simulations.
The ability of 1-alkyl-3-methylimidazolium ionic liquids, [Cnmim][X], to form layers at the air–water interface has been investigated systematically for the first time: five different chain lengths of the cation, n = 12, 14, 16, 18, 20 were studied, combined with three different anions, namely [N(Tf)2]−, [PF6]− and [Cl]−. The results show that only cations with chains longer than n = 16, combined with the [N(Tf)2]− anion form stable monolayers at the air/water interface, allowing measurable surface pressure vs area per molecule (π-A) isotherms immediately after spreading. The films of [C20mim][N(Tf)2] on water have been characterised using Brewster angle microscopy (BAM), Fourier transform infrared reflection absorption spectroscopy (FT-IRRAS), specular X-ray reflectivity (XRR) and grazing incidence X-ray diffraction (GIXD). Additionally, atomistic molecular dynamics simulations were also performed to obtain a molecular level interpretation of the experimental results. The results are compatible with a transition from an expanded monolayer to a trilayer structure, followed by the 3D collapse of the film. |
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AbstractList | The ability of 1-alkyl-3-methylimidazolium ionic liquids, [Cnmim][X], to form layers at the air–water interface has been investigated systematically for the first time: five different chain lengths of the cation, n = 12, 14, 16, 18, 20 were studied, combined with three different anions, namely [N(Tf)2]−, [PF6]− and [Cl]−. The results show that only cations with chains longer than n = 16, combined with the [N(Tf)2]− anion form stable monolayers at the air/water interface, allowing measurable surface pressure vs area per molecule (π-A) isotherms immediately after spreading. The films of [C20mim][N(Tf)2] on water have been characterised using Brewster angle microscopy (BAM), Fourier transform infrared reflection absorption spectroscopy (FT-IRRAS), specular X-ray reflectivity (XRR) and grazing incidence X-ray diffraction (GIXD). Additionally, atomistic molecular dynamics simulations were also performed to obtain a molecular level interpretation of the experimental results. The results are compatible with a transition from an expanded monolayer to a trilayer structure, followed by the 3D collapse of the film. Molecular dynamics simulations snapshots and electron density determined by X-ray reflectivity on layers of C20mimNTf2 ionic liquid at the air water interface undergoing a monolayer to trilayer transition with increase of surface density. [Display omitted] •1-alkyl-3-methylimidazolium ionic liquids with chain longer than 16 carbons and with NTF2 cation forms Langmuir monolayers.•For [C20mim][NTf2], X-ray diffraction reveal a transition from an expanded monolayer to a trilayer organized structure.•The monolayer to trilayer transition was reproduced by atomistic molecular dynamics simulations. The ability of 1-alkyl-3-methylimidazolium ionic liquids, [Cnmim][X], to form layers at the air–water interface has been investigated systematically for the first time: five different chain lengths of the cation, n = 12, 14, 16, 18, 20 were studied, combined with three different anions, namely [N(Tf)2]−, [PF6]− and [Cl]−. The results show that only cations with chains longer than n = 16, combined with the [N(Tf)2]− anion form stable monolayers at the air/water interface, allowing measurable surface pressure vs area per molecule (π-A) isotherms immediately after spreading. The films of [C20mim][N(Tf)2] on water have been characterised using Brewster angle microscopy (BAM), Fourier transform infrared reflection absorption spectroscopy (FT-IRRAS), specular X-ray reflectivity (XRR) and grazing incidence X-ray diffraction (GIXD). Additionally, atomistic molecular dynamics simulations were also performed to obtain a molecular level interpretation of the experimental results. The results are compatible with a transition from an expanded monolayer to a trilayer structure, followed by the 3D collapse of the film. |
ArticleNumber | 121028 |
Author | Eusébio, Tiago M. Rego, Tomás Valente, Raquel M. Ibrahim, Helen Fontaine, Philippe Taßler, Stephanie Morgado, Pedro Filipe, Eduardo J.M. Bonatout, Nathalie Goldmann, Michel |
Author_xml | – sequence: 1 givenname: Stephanie surname: Taßler fullname: Taßler, Stephanie organization: Synchrotron SOLEIL, L’Orme des Merisiers, Départementale 128, 91190, Saint-Aubin, France – sequence: 2 givenname: Nathalie surname: Bonatout fullname: Bonatout, Nathalie organization: Sorbonne Universités, Institut des NanoSciences de Paris, CNRS-UMR 7588, 4 Place Jussieu, 75005 Paris, France – sequence: 3 givenname: Tiago M. surname: Eusébio fullname: Eusébio, Tiago M. organization: Centro de Química Estrutural, Institute of Molecular Sciences, Departamento de Engenharia Química, Instituto Superior Técnico, Universidade de Lisboa, 1049-001 Lisboa, Portugal – sequence: 4 givenname: Raquel M. surname: Valente fullname: Valente, Raquel M. organization: Synchrotron SOLEIL, L’Orme des Merisiers, Départementale 128, 91190, Saint-Aubin, France – sequence: 5 givenname: Tomás surname: Rego fullname: Rego, Tomás organization: Sorbonne Universités, Institut des NanoSciences de Paris, CNRS-UMR 7588, 4 Place Jussieu, 75005 Paris, France – sequence: 6 givenname: Helen surname: Ibrahim fullname: Ibrahim, Helen organization: Sorbonne Universités, Institut des NanoSciences de Paris, CNRS-UMR 7588, 4 Place Jussieu, 75005 Paris, France – sequence: 7 givenname: Pedro surname: Morgado fullname: Morgado, Pedro organization: Centro de Química Estrutural, Institute of Molecular Sciences, Departamento de Engenharia Química, Instituto Superior Técnico, Universidade de Lisboa, 1049-001 Lisboa, Portugal – sequence: 8 givenname: Eduardo J.M. surname: Filipe fullname: Filipe, Eduardo J.M. organization: Centro de Química Estrutural, Institute of Molecular Sciences, Departamento de Engenharia Química, Instituto Superior Técnico, Universidade de Lisboa, 1049-001 Lisboa, Portugal – sequence: 9 givenname: Michel surname: Goldmann fullname: Goldmann, Michel organization: Synchrotron SOLEIL, L’Orme des Merisiers, Départementale 128, 91190, Saint-Aubin, France – sequence: 10 givenname: Philippe surname: Fontaine fullname: Fontaine, Philippe email: philippe.fontaine@synchrotron-soleil.fr organization: Synchrotron SOLEIL, L’Orme des Merisiers, Départementale 128, 91190, Saint-Aubin, France |
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Keywords | N(Tf)2 PF6 ESP Cnmim C18mim 1-Alkyl-3-methylimidazolium ionic liquids MD Simulations C16mim Cl C14mim XRD π-A-Isotherm BAM GIXD IRRAS arb. units C12mim LC cmc XRR LE Langmuir monolayer C20mim |
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Snippet | Molecular dynamics simulations snapshots and electron density determined by X-ray reflectivity on layers of C20mimNTf2 ionic liquid at the air water interface... The ability of 1-alkyl-3-methylimidazolium ionic liquids, [Cnmim][X], to form layers at the air–water interface has been investigated systematically for the... |
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SubjectTerms | 1-Alkyl-3-methylimidazolium ionic liquids Chemical Sciences Condensed Matter GIXD IRRAS Langmuir monolayer Material chemistry MD Simulations Physics XRR |
Title | Surface behaviour of 1-alkyl-3-methylimidazolium ionic liquids at the air-water interface |
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