Spectroscopic and theoretical study of (CF3SO2)2N- (TFSI-) and (CF3SO2)2NH (HTFSI)

被引:479
作者
Rey, I
Johansson, P
Lindgren, J
Lassègues, JC
Grondin, J
Servant, L
机构
[1] Univ Bordeaux 1, UMR 5803, Lab Physicochim Mol, F-33405 Talence, France
[2] Angstrom Lab, SE-75121 Uppsala, Sweden
关键词
D O I
10.1021/jp980375v
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The vibrational properties of the TFSI- anion solvated in a polymer or in water have been studied by comparing its IR and Raman spectra with those of the HTFSI molecule. Ab initio self-consistent field Hartree-Fock calculations have also been performed on the free ion or molecule to investigate their Mulliken charges, equilibrium geometry, and internal force constants. Both experimental and theoretical approaches confirm a pronounced delocalization of the negative charge on the nitrogen and oxygen atoms and a marked double-bond character of the SNS moiety for the anion. This double-bond character is decreased for the HTFSI molecule, leading to rather distinct frequencies for some specific vibrations such as the stretching motions of the SO2 and SNS groups. The agreement between experimental and calculated spectra is much better for HTFSI than for TFSI-. Tentative explanations are proposed for this difference.
引用
收藏
页码:3249 / 3258
页数:10
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