Dicationic ionic liquids (DILs) are a subclass of the ionic liquid (IL) family and are characterized by two cationic head groups linked by means of a spacer. While DILs are increasingly attracting interest due to their peculiar physico-chemical properties, there is still a lack of understanding of their intermolecular interactions. Herein, we report our investigations on the intermolecular vibrational modes of two bromide DILs and of a bistriflimide DIL. The minimal possible neutral cluster of ions was studied as a simplified model of these systems and was optimized at the DFT level. Normal modes of two sandwich-like conformers were then calculated using the harmonic approximation with analytical computation of the second derivatives of molecular energy with respect to the atomic coordinates. The calculated spectra were compared to far-infrared experimental spectra and two groups of peaks over three, for the two bromide DILs, and three over five, for the Tf2N- DIL, were described by the proposed neutral cluster model. Therefore, this model represents a reliable and computationally affordable model for the exploration of the intermolecular interactions of this kind of system.

An insight into the intermolecular vibrational modes of dicationic ionic liquids through far-infrared spectroscopy and DFT calculations

Guglielmero L.;Toncelli A.;Chiappe C.;Tredicucci A.;Pomelli C. S.
2019

Abstract

Dicationic ionic liquids (DILs) are a subclass of the ionic liquid (IL) family and are characterized by two cationic head groups linked by means of a spacer. While DILs are increasingly attracting interest due to their peculiar physico-chemical properties, there is still a lack of understanding of their intermolecular interactions. Herein, we report our investigations on the intermolecular vibrational modes of two bromide DILs and of a bistriflimide DIL. The minimal possible neutral cluster of ions was studied as a simplified model of these systems and was optimized at the DFT level. Normal modes of two sandwich-like conformers were then calculated using the harmonic approximation with analytical computation of the second derivatives of molecular energy with respect to the atomic coordinates. The calculated spectra were compared to far-infrared experimental spectra and two groups of peaks over three, for the two bromide DILs, and three over five, for the Tf2N- DIL, were described by the proposed neutral cluster model. Therefore, this model represents a reliable and computationally affordable model for the exploration of the intermolecular interactions of this kind of system.
2019
Settore FIS/03 - Fisica della Materia
Ionic liquids; DFT; far-infrared
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11384/84528
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