Distance Angle Descriptors of the Interionic and Ion-Solvent Interactions in Imidazolium-Based Ionic Liquid Mixtures with Aprotic Solvents: A Molecular Dynamics Simulation Study

Volodymyr A. Koverga, Yevheniia Smortsova, François Alexandre Miannay, Oleg N. Kalugin, Toshiyuki Takamuku, P. Jedlovszky, Bogdan Marekha, M. Natalia D.S. Cordeiro, Abdenacer Idrissi

Research output: Contribution to journalArticle

Abstract

The aim of this paper is to quantify the changes of the interionic and ion-solvent interactions in mixtures of imidazolium-based ionic liquids, having tetrafluoroborate (BmimBF4), hexafluorophosphate (BmimPF6), trifluoromethylsulfonate (BmimTFO), or bis(trifluoromethanesulfonyl)imide (BmimTFSI), anions, and polar aprotic molecular solvents, such as acetonitrile (AN), Î-butyrolactone (GBL), and propylene carbonate (PC). For this purpose, we calculate, using the nearest-neighbor approach, the average distance between the imidazolium ring H atom in positions 2, 4, and 5 (H2,4,5) and the nearest high-electronegativity atom of the solvent or anion (X) as distance descriptors, and the mean angle formed by the C2,4,5-H2,4,5 bond and the H2,4,5···X axis around the H2,4,5 atom as angular descriptors of the cation-anion and cation-solvent interactions around the ring C-H groups. The behavior of these descriptors as a function of the ionic liquid mole fraction is analyzed in detail. The obtained results show that the extent of the change of these descriptors with respect to their values in the neat ionic liquid depends both on the nature of the anion and on the mixture composition. Thus, in the case of the mixtures of the molecular solvents with BmimBF4 and BmimTFO, a small change of the distance and a drastic increase of the angular descriptor corresponding to the cation-anion interactions are observed with decreasing mole fraction of the ionic liquid, indicating that the anion moves from the above/below position (with respect to the imidazolium ring plane) to a position that is nearly linearly aligned with the C2-H2 bond and hinders the possible interaction between the C2-H2 group and the solvent molecules. On the other hand, in the case of mixtures of BmimTFSI and BmimPF6 with the molecular solvents, both the observed increase of the distance descriptor and the slight change of the angular descriptor with decreasing ionic liquid mole fraction are compatible with the direct interactions of the solvent with the C2-H2 group. The behavior of these descriptors is correlated with the experimentally observed 1H chemical shift of the C2-H2 group and the red shift of the C2-H2 vibrational mode, particularly at low ionic liquid mole fractions. The present results are thus of great help in interpreting these experimental observations.

Original languageEnglish
Pages (from-to)6065-6075
Number of pages11
JournalJournal of Physical Chemistry B
Volume123
Issue number28
DOIs
Publication statusPublished - Jun 9 2019

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Ionic Liquids
Molecular Dynamics Simulation
Ionic liquids
Molecular dynamics
Ions
molecular dynamics
Anions
Negative ions
Computer simulation
liquids
anions
ions
simulation
interactions
Cations
Positive ions
imides
cations
Atoms
rings

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry

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Distance Angle Descriptors of the Interionic and Ion-Solvent Interactions in Imidazolium-Based Ionic Liquid Mixtures with Aprotic Solvents : A Molecular Dynamics Simulation Study. / Koverga, Volodymyr A.; Smortsova, Yevheniia; Miannay, François Alexandre; Kalugin, Oleg N.; Takamuku, Toshiyuki; Jedlovszky, P.; Marekha, Bogdan; Cordeiro, M. Natalia D.S.; Idrissi, Abdenacer.

In: Journal of Physical Chemistry B, Vol. 123, No. 28, 09.06.2019, p. 6065-6075.

Research output: Contribution to journalArticle

Koverga, Volodymyr A. ; Smortsova, Yevheniia ; Miannay, François Alexandre ; Kalugin, Oleg N. ; Takamuku, Toshiyuki ; Jedlovszky, P. ; Marekha, Bogdan ; Cordeiro, M. Natalia D.S. ; Idrissi, Abdenacer. / Distance Angle Descriptors of the Interionic and Ion-Solvent Interactions in Imidazolium-Based Ionic Liquid Mixtures with Aprotic Solvents : A Molecular Dynamics Simulation Study. In: Journal of Physical Chemistry B. 2019 ; Vol. 123, No. 28. pp. 6065-6075.
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abstract = "The aim of this paper is to quantify the changes of the interionic and ion-solvent interactions in mixtures of imidazolium-based ionic liquids, having tetrafluoroborate (BmimBF4), hexafluorophosphate (BmimPF6), trifluoromethylsulfonate (BmimTFO), or bis(trifluoromethanesulfonyl)imide (BmimTFSI), anions, and polar aprotic molecular solvents, such as acetonitrile (AN), {\^I}-butyrolactone (GBL), and propylene carbonate (PC). For this purpose, we calculate, using the nearest-neighbor approach, the average distance between the imidazolium ring H atom in positions 2, 4, and 5 (H2,4,5) and the nearest high-electronegativity atom of the solvent or anion (X) as distance descriptors, and the mean angle formed by the C2,4,5-H2,4,5 bond and the H2,4,5···X axis around the H2,4,5 atom as angular descriptors of the cation-anion and cation-solvent interactions around the ring C-H groups. The behavior of these descriptors as a function of the ionic liquid mole fraction is analyzed in detail. The obtained results show that the extent of the change of these descriptors with respect to their values in the neat ionic liquid depends both on the nature of the anion and on the mixture composition. Thus, in the case of the mixtures of the molecular solvents with BmimBF4 and BmimTFO, a small change of the distance and a drastic increase of the angular descriptor corresponding to the cation-anion interactions are observed with decreasing mole fraction of the ionic liquid, indicating that the anion moves from the above/below position (with respect to the imidazolium ring plane) to a position that is nearly linearly aligned with the C2-H2 bond and hinders the possible interaction between the C2-H2 group and the solvent molecules. On the other hand, in the case of mixtures of BmimTFSI and BmimPF6 with the molecular solvents, both the observed increase of the distance descriptor and the slight change of the angular descriptor with decreasing ionic liquid mole fraction are compatible with the direct interactions of the solvent with the C2-H2 group. The behavior of these descriptors is correlated with the experimentally observed 1H chemical shift of the C2-H2 group and the red shift of the C2-H2 vibrational mode, particularly at low ionic liquid mole fractions. The present results are thus of great help in interpreting these experimental observations.",
author = "Koverga, {Volodymyr A.} and Yevheniia Smortsova and Miannay, {Fran{\cc}ois Alexandre} and Kalugin, {Oleg N.} and Toshiyuki Takamuku and P. Jedlovszky and Bogdan Marekha and Cordeiro, {M. Natalia D.S.} and Abdenacer Idrissi",
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T1 - Distance Angle Descriptors of the Interionic and Ion-Solvent Interactions in Imidazolium-Based Ionic Liquid Mixtures with Aprotic Solvents

T2 - A Molecular Dynamics Simulation Study

AU - Koverga, Volodymyr A.

AU - Smortsova, Yevheniia

AU - Miannay, François Alexandre

AU - Kalugin, Oleg N.

AU - Takamuku, Toshiyuki

AU - Jedlovszky, P.

AU - Marekha, Bogdan

AU - Cordeiro, M. Natalia D.S.

AU - Idrissi, Abdenacer

PY - 2019/6/9

Y1 - 2019/6/9

N2 - The aim of this paper is to quantify the changes of the interionic and ion-solvent interactions in mixtures of imidazolium-based ionic liquids, having tetrafluoroborate (BmimBF4), hexafluorophosphate (BmimPF6), trifluoromethylsulfonate (BmimTFO), or bis(trifluoromethanesulfonyl)imide (BmimTFSI), anions, and polar aprotic molecular solvents, such as acetonitrile (AN), Î-butyrolactone (GBL), and propylene carbonate (PC). For this purpose, we calculate, using the nearest-neighbor approach, the average distance between the imidazolium ring H atom in positions 2, 4, and 5 (H2,4,5) and the nearest high-electronegativity atom of the solvent or anion (X) as distance descriptors, and the mean angle formed by the C2,4,5-H2,4,5 bond and the H2,4,5···X axis around the H2,4,5 atom as angular descriptors of the cation-anion and cation-solvent interactions around the ring C-H groups. The behavior of these descriptors as a function of the ionic liquid mole fraction is analyzed in detail. The obtained results show that the extent of the change of these descriptors with respect to their values in the neat ionic liquid depends both on the nature of the anion and on the mixture composition. Thus, in the case of the mixtures of the molecular solvents with BmimBF4 and BmimTFO, a small change of the distance and a drastic increase of the angular descriptor corresponding to the cation-anion interactions are observed with decreasing mole fraction of the ionic liquid, indicating that the anion moves from the above/below position (with respect to the imidazolium ring plane) to a position that is nearly linearly aligned with the C2-H2 bond and hinders the possible interaction between the C2-H2 group and the solvent molecules. On the other hand, in the case of mixtures of BmimTFSI and BmimPF6 with the molecular solvents, both the observed increase of the distance descriptor and the slight change of the angular descriptor with decreasing ionic liquid mole fraction are compatible with the direct interactions of the solvent with the C2-H2 group. The behavior of these descriptors is correlated with the experimentally observed 1H chemical shift of the C2-H2 group and the red shift of the C2-H2 vibrational mode, particularly at low ionic liquid mole fractions. The present results are thus of great help in interpreting these experimental observations.

AB - The aim of this paper is to quantify the changes of the interionic and ion-solvent interactions in mixtures of imidazolium-based ionic liquids, having tetrafluoroborate (BmimBF4), hexafluorophosphate (BmimPF6), trifluoromethylsulfonate (BmimTFO), or bis(trifluoromethanesulfonyl)imide (BmimTFSI), anions, and polar aprotic molecular solvents, such as acetonitrile (AN), Î-butyrolactone (GBL), and propylene carbonate (PC). For this purpose, we calculate, using the nearest-neighbor approach, the average distance between the imidazolium ring H atom in positions 2, 4, and 5 (H2,4,5) and the nearest high-electronegativity atom of the solvent or anion (X) as distance descriptors, and the mean angle formed by the C2,4,5-H2,4,5 bond and the H2,4,5···X axis around the H2,4,5 atom as angular descriptors of the cation-anion and cation-solvent interactions around the ring C-H groups. The behavior of these descriptors as a function of the ionic liquid mole fraction is analyzed in detail. The obtained results show that the extent of the change of these descriptors with respect to their values in the neat ionic liquid depends both on the nature of the anion and on the mixture composition. Thus, in the case of the mixtures of the molecular solvents with BmimBF4 and BmimTFO, a small change of the distance and a drastic increase of the angular descriptor corresponding to the cation-anion interactions are observed with decreasing mole fraction of the ionic liquid, indicating that the anion moves from the above/below position (with respect to the imidazolium ring plane) to a position that is nearly linearly aligned with the C2-H2 bond and hinders the possible interaction between the C2-H2 group and the solvent molecules. On the other hand, in the case of mixtures of BmimTFSI and BmimPF6 with the molecular solvents, both the observed increase of the distance descriptor and the slight change of the angular descriptor with decreasing ionic liquid mole fraction are compatible with the direct interactions of the solvent with the C2-H2 group. The behavior of these descriptors is correlated with the experimentally observed 1H chemical shift of the C2-H2 group and the red shift of the C2-H2 vibrational mode, particularly at low ionic liquid mole fractions. The present results are thus of great help in interpreting these experimental observations.

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