The Raman spectra for 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide [BMI][TFSA] containing alkaline metal salts of TFSA
-, MTFSA (M = Li, Na, K and Cs), were recorded in the frequency range of 200 - 1800 cm
-1, with varying salt concentrations at 298 K. With Li
+ and Na
+ ions, at the frequency range of 730 - 760 cm
-1, new Raman bands ascribable to the anion bound to the ions appeared at higher frequency relative to that found in the neat ionic liquid. On the other hand, with K
+ and Cs
+ ions, single Raman bands were solely observed. According to the difference Raman spectra for the ionic liquids containing K
+ and Cs
+, evaluated by subtracting Raman spectra for the neat ionic liquid, it turned out that two-state approximation,
i.e., bulk TFSA
- and TFSA
- bound to K
+ and Cs
+ ions, could hold, as Li
+ and Na
+ ions. By careful analyses of Raman band intensity arising from bulk TFSA
- as a function of the salt concentration, the solvation numbers for the respective ions were successfully evaluated to be 1.95 for Li
+, 2.88 for Na
+, 3.2 for K
+ and 3.9 for Cs
+, respectively. By taking into account that TFSA
- acts as a bidentate ligand, the atomic coordination numbers are proposed to be 4, 6, 6 and 8 for Li
+, Na
+, K
+ and Cs
+, respectively. Raman shifts for the TFSA
- bound to the metal ions relative to that of the bulk TFSA
- were plotted against the ionic radii for the solvated alkaline metal ions estimated
via Shannon's ionic radii, to yield a straight line with a slope of almost unity, suggesting that the electrostatic interaction predominantly operates in the ion-ion interaction between the alkaline metal ions and TFSA
-, as expected. Moreover, the Raman spectra in the frequency range of 370 - 450 cm
-1 strongly depend on the alkaline metal ions, indicating that
cis TFSA
- is favored in the first solvation sphere of the Li
+ ion of a relatively small ionic radius, and that such a preferred conformational isomerism of TFSA
- diminishes with an increase of the ionic radii of the central metal ions.
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