Journal
JOURNAL OF PHYSICAL CHEMISTRY B
Volume 112, Issue 38, Pages 11936-11941Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jp8021908
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Funding
- Grants-in-Aid for Scientific Research [14COEB01, 14GS0213, 18550025]
- Ministry of Education, Culture, Sports, Science and Technology of Japan
- Hanyang University
- Seoul Research and Business Development Program [10816]
- National Research Foundation of Korea [R11-2002-099-06001-0] Funding Source: Korea Institute of Science & Technology Information (KISTI), National Science & Technology Information Service (NTIS)
- Grants-in-Aid for Scientific Research [18550025, 14GS0213] Funding Source: KAKEN
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The air/liquid interface of a room temperature ionic liquid, 1-butyl-3-methylimidazolium trifluoromethane-sulfonate ([bmim]OTf), is investigated using infrared-visible sum frequency generation (SFG) spectroscopy. The SFG spectra clearly show low-frequency modes [CF3-symmetric stretching (ss) mode and SO3-symmetric stretching (ss) mode] of the OTf anion, demonstrating the existence of anions polar oriented at the interface. The amplitude of the CF3-ss peak of the OTf anion has the opposite sign with respect to that of the SO3-ss peak, indicating that OTf anions at the surface have polar ordering where the nonpolar CF3 group points away from the bulk into the air, whereas the SO3 group points toward the bulk liquid. The line width of the SFG peak from the submerged SO3 group is appreciably narrower than that from IR absorption, suggesting the environment of the surface OTf anions is much more homogeneous than that of the bulk. The vibrational calculations also suggest that the anions and the cations form a more specific aggregated configuration at the surface as compared to the bulk.
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