期刊
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
卷 22, 期 22, 页码 12565-12576出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/d0cp01219j
关键词
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资金
- Ministry of Education, Culture, Sports, Science and Technology (MEXT) of Japan [26248004, 16H04095]
- National Research Foundation (NRF) of the Republic of Korea [2019R1A2C1004292]
- National Research Foundation of Korea [2019R1A2C1004292] Funding Source: Korea Institute of Science & Technology Information (KISTI), National Science & Technology Information Service (NTIS)
- Grants-in-Aid for Scientific Research [16H04095, 26248004] Funding Source: KAKEN
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 ([C(n)mim](+);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 CH(3)group) of the [C(n)mim](+)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 [C(n)mim](+)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.
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