Application of Density Functional Theory and Vibrational Spectroscopy Toward the Rational Design of Ionic Liquids

D. functional theory methods in combination with vibrational spectroscopy are used to investigate possible variants of mol. structure of the ion pairs of several imidazolium-based ionic liqs. (ILs). Multiple stable structures are detd. with the anion positioned (a) near to the C2 atom of the imidazolium ring, (b) between N1 and C5, (c) between N3 and C4, and (d) between C4 and C5. Chloride and bromide anions in vacuum also occupy positions above or below the imidazolium ring, but in the condensed state these positions are destabilized. In comparison with the halides that almost equally occupy the positions (a-d), tetrafluoroborate and hexafluorophosphate anions strongly prefer position (a). The position and the type of the anion influence the conformation of the side chains bound to the imidazolium N1 atom, which are able to adopt in vacuum all usual staggered or eclipsed conformations, although in the liq. state some of the conformations are present only as minor forms if at all. Vibrations of the cations depend both on the conformational changes and on the assocn. with the anion. The formation of the ion pairs influences mainly stretching and out-of-plane vibrations of the imidazolium C-H groups and stretching vibrations of the perfluoroanions. Other modes of the ions retain their individuality and practically do not mix. This allows "interionic" vibrations to be sepd. and to regard the couple of the ions as an anharmonic oscillator. Such a model correlates the mol. structure of various ILs and their m.ps. without involving the energy of the interaction between the cations and anions but explains structure-m.p. correlations on the grounds of quasy-elastic properties

Molecular structure, vibrational spectra, and hydrogen bonding of the ionic liquid 1-ethyl-3methyl-1H-imidazolium tetrafluoroborate

The IR and Raman spectra and conformations of the ionic liquid 1-ethyl-3-methyl-1H-imidazolium tetrafluoroborate, [EMIM][BF4] (6), were analyzed within the framework of scaled quantum mechanics (SQM). It was shown that SQM successfully reproduced the spectra of the ionic liquid. The computations revealed that normal modes of the EMIM+ (.) BF4- ion pair closely resemble those of the isolated ions EMIM+ and BF4-, except for the antisymmetric BF stretching vibrations of the anion, and the out-of-plane and stretching vibrations of the H-C(2) moiety of the cation. The most plausible explanation for the pronounced changes of the latter vibrations upon ion-pair formation is the H-bonding between H-C(2) and BF4-. However, these weak H-bonds are of minor importance compared with the Coulomb interactions between the ions that keep them closely associated even in dilute CD2Cl2 Solutions. According to the 'gas-phase' computations, in these associates, the BF4- anion is positioned over the imidazolium ring of the EMIM+ cation and has short contacts not only with the H-C(2) of the latter, but also with a proton of the Me-N(3) group