Bi-layering at ionic liquid surfaces: a sum-frequency generation vibrational spectroscopy- And molecular dynamics simulation-based study

Takashi Iwahashi, Tatsuya Ishiyama, Yasunari Sakai, Akihiro Morita, Doseok Kim, Yukio Ouchi

研究成果: Article査読

抄録

Room-temperature ionic liquids (RTILs) are being increasingly employed as novel solvents in several fields, including chemical engineering, electrochemistry, and synthetic chemistry. To further increase their usage potential, a better understanding of the structure of their surface layer is essential. Bi-layering at the surfaces of RTILs consisting of 1-alkyl-3-methylimidazolium ([Cnmim]+;n= 4, 6, 8, 10, and 12) cations and bis(trifluoromethanesulfonyl)amide ([TFSA]) anions was demonstratedviainfrared-visible sum-frequency generation (IV-SFG) vibrational spectroscopy and molecular dynamics (MD) simulations. It was found that the sum-frequency (SF) signal from the [TFSA]anions decreases as the alkyl chain length increases, whereas the SF signal from the r+mode (the terminal CH3group) of the [Cnmim]+cations is almost the same regardless of chain length. MD simulations show the formation of a bi-layered structure consisting of the outermost first layer and a submerged second layer in a “head-to-head” molecular arrangement. The decrease in the SF signals of the normal modes of the [TFSA]anions is caused by destructive and out-of-phase interference of vibrations of corresponding molecular moieties oriented toward each other in the first and second layers. In contrast, the r+mode of [Cnmim]+does not experience destructive interference because the peak position of the r+mode differs marginally at the surface and in the bulk. Our conclusions are not limited to the system presented here. Similar bi-layered structures can be expected for the surfaces of conventional RTILs, which necessitates the consideration of bi-layering in the design and application.

本文言語English
ページ(範囲)12565-12576
ページ数12
ジャーナルPhysical Chemistry Chemical Physics
22
22
DOI
出版ステータスPublished - 2020 6 14

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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