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Femtosecond Raman-Induced Kerr Effect Study of Temperature-Dependent Intermolecular Dynamics in Molten Bis(trifluoromethylsulfonyl)amide Salts: Effects of Cation Species

Cite this: J. Phys. Chem. B 2018, 122, 22, 6033–6047
Publication Date (Web):May 10, 2018
https://doi.org/10.1021/acs.jpcb.8b03302
Copyright © 2018 American Chemical Society

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    Abstract

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    In this study, we have investigated the effects of cation structures on the temperature dependence of the intermolecular vibrational dynamics of ionic liquids using femtosecond Raman-induced Kerr effect spectroscopy. The ionic liquids used in this study are bis(trifluoromethylsulfonyl)amide [NTf2] salts of the cations 1-butyl-3-methylimidazolium [C4MIm]+, 1-butyl-1-methylpyrrolidinium [Pyrr14]+, 1-butylpyridinium [C4Py]+, butyldiethylmethylammonium [N1224]+, triethyloctylammonium [N2228]+, and triethyloctylphosphonium [P2228]+. All of the ionic liquids show temperature-dependent low-frequency spectra. A difference in the temperature dependence between the spectra of the aromatic and nonaromatic cation based ionic liquids is especially significant. In the case of the aromatic cation based ionic liquids [C4MIm][NTf2] and [C4Py][NTf2], the spectral intensities in the low-frequency region below ca. 50 cm–1 increase and the high-frequency components at ca. 80 cm–1 shift to lower frequencies with rising temperature. In contrast, the ionic liquids based on nonaromatic cations only exhibit an increase in the low-frequency region below ca. 50 cm–1 with increasing temperature, while the high-frequency region of the spectra above ca. 50 cm–1 shows little change with variation of the temperature. These results suggest that the presence or absence of aromatic rings is the main factor in determining the temperature-dependent spectral features, particularly in the high-frequency region. We also found that the alkyl chain length and central atoms of the nonaromatic quaternary cations do not have much influence on the temperature-dependent spectral features. The first moments of the aromatic cation based ionic liquids are a little more sensitive to temperature than those of the nonaromatic cation based ionic liquids. The temperature-dependent viscosities and fragilities of the ionic liquids have also been examined.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jpcb.8b03302.

    • Details of synthesis procedures of ILs synthesized in this study, line shape analysis results of Kerr spectra of ILs, temperature-dependent Kerr transients of molecular liquids, lists of fit parameters for the Kerr transients of molecular liquids, line shape analysis results of the Kerr spectra of ILs and molecular liquids, and temperature-dependent viscosity data of ILs (PDF)

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    This article is cited by 14 publications.

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    2. Masako Shimizu, Hideaki Shirota. Intermolecular Dynamics of Positively and Negatively Charged Aromatics and Their Isoelectronic Neutral Analogs in Aqueous Solutions. The Journal of Physical Chemistry B 2022, 126 (23) , 4309-4323. https://doi.org/10.1021/acs.jpcb.2c01517
    3. Masatoshi Ando, Hideaki Shirota. Low-Frequency Spectra of 1-Methyl-3-octylimidazolium Tetrafluoroborate Mixtures with Poly(ethylene glycol) by Femtosecond Raman-Induced Kerr Effect Spectroscopy. The Journal of Physical Chemistry B 2021, 125 (43) , 12006-12019. https://doi.org/10.1021/acs.jpcb.1c07079
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    7. Shohei Kakinuma, Hideaki Shirota. Femtosecond Raman-Induced Kerr Effect Study of Temperature-Dependent Intermolecular Dynamics in Pyrrolidinium-Based Ionic Liquids: Effects of Anion Species. The Journal of Physical Chemistry B 2019, 123 (6) , 1307-1323. https://doi.org/10.1021/acs.jpcb.8b10269
    8. Miaoling Yang, Hao Zhang, Yuan Yao, Wei Lin, Shaoxiang Duan, Bo Liu. Characterization of Light-Sensitive Refractive Indices for Ionic Liquids Based on a Coreless-Fiber-Coupled Microcavity Interferometric Sensor. IEEE Sensors Journal 2023, 23 (13) , 14142-14152. https://doi.org/10.1109/JSEN.2023.3276889
    9. İlhan CANDAN. Raman Excitation of Hydrogen Molecules to v = 1 State. Iğdır Üniversitesi Fen Bilimleri Enstitüsü Dergisi 2021, 11 (2) , 1068-1079. https://doi.org/10.21597/jist.828194
    10. Julia Leier, Nadine C. Michenfelder, Andreas‐Neil Unterreiner. Understanding the Photoexcitation of Room Temperature Ionic Liquids. ChemistryOpen 2021, 10 (2) , 72-82. https://doi.org/10.1002/open.202000278
    11. Hideaki Shirota, Shohei Kakinuma. Temperature-dependent features in low-frequency spectra of ionic liquids. 2021, 159-187. https://doi.org/10.1016/B978-0-12-820280-7.00001-2
    12. Hideaki Shirota. Intermolecular Vibrations in Aprotic Molecular Liquids and Ionic Liquids. 2021, 195-229. https://doi.org/10.1007/978-981-16-5395-7_7
    13. Hideaki Shirota, Masatoshi Ando, Shohei Kakinuma, Kotaro Takahashi. Ultrafast Dynamics in Nonaromatic Cation Based Ionic Liquids: A Femtosecond Raman-Induced Kerr Effect Spectroscopic Study. Bulletin of the Chemical Society of Japan 2020, 93 (12) , 1520-1539. https://doi.org/10.1246/bcsj.20200198
    14. Yuko Amo, Takuya Hasegawa Sato, Yasuo Kameda, Takeshi Usuki. Lowest frequency mode in Raman susceptibility: 2-propanol from ambient to supercritical condition. The European Physical Journal B 2020, 93 (1) https://doi.org/10.1140/epjb/e2019-100145-1

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