Atom Substitution Effects in Ionic Liquids: A Microscopic View by Femtosecond Raman-Induced Kerr Effect Spectroscopy

Shirota, Hideaki; Fukazawa, Hiroki

doi:10.5772/14817

Cited by 29 publications

(45 citation statements)

References 75 publications

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“…We have previously studied the effect of heavy atom substitution in constituent ions of ILs on η, extensively . In ion species, whether they are aromatic or nonaromatic cations, or anions, , the IL η decreases when an element is substituted with a heavier one (higher period in the same family).…”

Section: Resultsmentioning

confidence: 99%

“…26 We have previously studied the effect of heavy atom substitution in constituent ions of ILs on η, extensively. 34 In Table 2. Formula Weights, FW, Liquid Densities, ρ, and Molar Volumes, V m at 293 K and Atmospheric Pressure (0.1 MPa) for Phosphonium-Based ILs ion species, whether they are aromatic 35 or nonaromatic cations, 18 or anions, 18,36 the IL η decreases when an element is substituted with a heavier one (higher period in the same family).…”

Section: The Newly Synthesized Ils In This Study Are Triethyl-[ ( M E...mentioning

confidence: 99%

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Liquid Properties of Ionic Liquids Based on Phosphonium Cations with (Alkylthio)alkyl Groups

et al. 2019

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Herein, we report the liquid properties, that is, densities, viscosities, electrical conductivities, surface tensions, melting points, and glass transition temperatures, of 18 novel sulfur-containing phosphonium cation- (triethyl[(methylthio)methyl]phosphonium, triethyl[2-(methylthio)ethyl]phosphonium, triethyl[2-(ethylthio)ethyl]phosphonium, tributyl[(methylthio)methyl]phosphonium, tributyl[2-(methylthio)ethyl]phosphonium, tributyl[2-(ethylthio)ethyl]phosphonium) based ionic liquids with bis(trifluoromethylsulfonyl)amide, bis(fluorosulfonyl)amide, and tetrafluoroborate anions. The effects of the (alkylthio)alkyl groups on the viscosity and surface tension of the ionic liquids are very different from those of common alkyl groups in typical ionic liquids.

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Section: Resultsmentioning

confidence: 99%

Section: The Newly Synthesized Ils In This Study Are Triethyl-[ ( M E...mentioning

confidence: 99%

Liquid Properties of Ionic Liquids Based on Phosphonium Cations with (Alkylthio)alkyl Groups

et al. 2019

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“…This approach is effective because the molecular motions in this frequency region include intermolecular vibrations, which are sensitive to the intermolecular interactions and the structure at the molecular level. Femtosecond Raman-induced Kerr effect spectroscopy (fs-RIKES) provides high-quality spectra in this frequency region (typically 0.3–300 cm –1 ). , Accordingly, fs-RIKES has been employed to study the low-frequency vibrational motions in simple MLs − as well as complicated systems, − including ILs. − …”

Section: Introductionmentioning

confidence: 99%

Low-Frequency Spectra of 1-Methyl-3-octylimidazolium Tetrafluoroborate Mixtures with Methanol, Acetonitrile, and Dimethyl Sulfoxide: A Combined Study of Femtosecond Raman-Induced Kerr Effect Spectroscopy and Molecular Dynamics Simulations

et al. 2020

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In this study, we examined the low-frequency spectra of 1-methyl-3-octylimidazolium tetrafluoroborate ([MOIm][BF4]) mixtures with methanol (MeOH), acetonitrile (MeCN), and dimethyl sulfoxide (DMSO), which were obtained by femtosecond Raman-induced Kerr effect spectroscopy (fs-RIKES) and molecular dynamics (MD) simulations. In addition, we estimated the liquid properties of the mixtures, such as density ρ, surface tension γ, viscosity η, and electrical conductivity σ. The line shapes of the low-frequency Kerr spectra of the three [MOIm][BF4] mixture systems strongly depend on the mole fraction of the molecular liquid, X ML. The spectral intensity increases with increasing X ML of the [MOIm][BF4]/MeCN system but decreases for the [MOIm][BF4]/MeOH and [MOIm][BF4]/DMSO systems. These behaviors of the spectral intensities reasonably agree with the vibrational density-of-states spectra when the polarizability anisotropies of MeOH, MeCN, DMSO, and ion species are considered. The characteristic frequencies (first moments, M 1) of the low-frequency spectra of the three mixture systems are almost insensitive at X ML = 0–0.6. However, the frequencies vary mildly at X ML = 0.6–0.9 and dramatically at X ML = 0.9–1. The X ML-dependent M 1 in the Kerr spectra are well reproduced by the MD simulations. Plots of M 1 versus bulk parameter, (γ/ρ)1/2, for the three mixture systems show that the mixtures at X ML = 0–0.6 behave like aromatic cation-based ionic liquids (ILs), those at X ML = 0.9–1 are molecular liquids (MLs), and those at X ML = 0.6–0.9 are transitioning between aromatic cation-based ILs and MLs. MD simulations show that the solvent molecules localized at the interface between the ionic and the alkyl group regions without forming large solvent networks at X ML = 0–0.6. However, solvent networks or regions develop largely at X ML = 0.6–0.9 and the constituent ions of the IL disperse in the MLs at X ML = 0.9–1. The MD simulations corroborate the results obtained by fs-RIKES.

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“…9 The use of ionic liquids in electrochemical devices is driven by their unique physical properties, such as low melting points, low vapor pressure, non-flammability, thermal and chemical stability, and broad electrochemical window. 10,11 However, one of the most desired feature of these media is their high electric conductivity (s). Therefore, in the last few years many efforts have been dedicated to understanding the conductivity mechanism in ion-containing systems and consequently to predict the s behavior under various thermodynamic conditions.…”

Section: Introductionmentioning

confidence: 99%

On the scaling behavior of electric conductivity in [C₄mim][NTf₂]

Wojnarowska

Jarosz

Grzybowski

et al. 2014

Phys. Chem. Chem. Phys.

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In this work we examine, for the first time, the molar conductivity behavior of the deeply supercooled room temperature ionic liquid [C4mim][NTf2] in the temperature, pressure and volume thermodynamic space in terms of density scaling (TV(γ))(-1) combined with the equation of state (EOS). The exponent γσ determined from the Avramov model analysis is compared with the coefficient obtained from the viscosity studies carried out at moderate temperatures. Therefore, the experimental results presented herein provide the answer to the long-standing question regarding the validity of thermodynamic scaling of ionic liquids over a wide temperature range, i.e. from the normal liquid state to the glass transition point. Finally, we investigate the relationship between the dynamic and thermodynamic properties of [C4mim][NTf2] represented by scaling exponent γ and Grüneisen constant γG, respectively.

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Atom Substitution Effects in Ionic Liquids: A Microscopic View by Femtosecond Raman-Induced Kerr Effect Spectroscopy

Cited by 29 publications

References 75 publications

Liquid Properties of Ionic Liquids Based on Phosphonium Cations with (Alkylthio)alkyl Groups

Liquid Properties of Ionic Liquids Based on Phosphonium Cations with (Alkylthio)alkyl Groups

Low-Frequency Spectra of 1-Methyl-3-octylimidazolium Tetrafluoroborate Mixtures with Methanol, Acetonitrile, and Dimethyl Sulfoxide: A Combined Study of Femtosecond Raman-Induced Kerr Effect Spectroscopy and Molecular Dynamics Simulations

On the scaling behavior of electric conductivity in [C₄mim][NTf₂]

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Atom Substitution Effects in Ionic Liquids: A Microscopic View by Femtosecond Raman-Induced Kerr Effect Spectroscopy

Cited by 29 publications

References 75 publications

Liquid Properties of Ionic Liquids Based on Phosphonium Cations with (Alkylthio)alkyl Groups

Liquid Properties of Ionic Liquids Based on Phosphonium Cations with (Alkylthio)alkyl Groups

Low-Frequency Spectra of 1-Methyl-3-octylimidazolium Tetrafluoroborate Mixtures with Methanol, Acetonitrile, and Dimethyl Sulfoxide: A Combined Study of Femtosecond Raman-Induced Kerr Effect Spectroscopy and Molecular Dynamics Simulations

On the scaling behavior of electric conductivity in [C4mim][NTf2]

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On the scaling behavior of electric conductivity in [C₄mim][NTf₂]