Ion-Solvent Interactions in Acetonitrile Solutions of Lithium Iodide and Tetrabutylammonium Iodide

Andrew K. Mollner, Paula A. Brooksby, John S. Loring, I. Bakó, G. Pálinkás, W. Ronald Fawcett

Research output: Contribution to journalArticle

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Abstract

The vibrational spectra of acetonitrile solutions containing lithium iodide and tetrabutylammonium iodide have been studied using ATR-FTIR spectroscopy. The focus of interest was the effect of the iodide anion on the important vibrational bands of acetonitrile. The main effect of the LiI electrolyte is to shift the C≡N stretching frequency in the blue direction due to interaction of the Li + cation with the electronegative C≡N group. However, a small red shift of the C≡N stretching mode due to the interaction of I - with the methyl group of acetonitrile is found in both electrolytes. On the other hand, the symmetic and asymmetric stretching modes of the methyl group are significantly red shifted in the presence of LiI. Ab initio quantum chemical calculations were carried out to determine the optimum location of the Li + and I - ions in ion-solvent complexes containing a varying number of solvent molecules. These calculations correctly predict the direction of the observed shifts for all the principal bands of acetonitrile except the methyl stretching modes.

Original languageEnglish
Pages (from-to)3344-3349
Number of pages6
JournalJournal of Physical Chemistry A
Volume108
Issue number16
DOIs
Publication statusPublished - Apr 22 2004

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Lithium
iodides
Stretching
acetonitrile
lithium
Ions
Electrolytes
ions
interactions
electrolytes
shift
Iodides
Vibrational spectra
red shift
vibrational spectra
Anions
Cations
Spectroscopy
anions
cations

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Ion-Solvent Interactions in Acetonitrile Solutions of Lithium Iodide and Tetrabutylammonium Iodide. / Mollner, Andrew K.; Brooksby, Paula A.; Loring, John S.; Bakó, I.; Pálinkás, G.; Ronald Fawcett, W.

In: Journal of Physical Chemistry A, Vol. 108, No. 16, 22.04.2004, p. 3344-3349.

Research output: Contribution to journalArticle

Mollner, Andrew K. ; Brooksby, Paula A. ; Loring, John S. ; Bakó, I. ; Pálinkás, G. ; Ronald Fawcett, W. / Ion-Solvent Interactions in Acetonitrile Solutions of Lithium Iodide and Tetrabutylammonium Iodide. In: Journal of Physical Chemistry A. 2004 ; Vol. 108, No. 16. pp. 3344-3349.
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abstract = "The vibrational spectra of acetonitrile solutions containing lithium iodide and tetrabutylammonium iodide have been studied using ATR-FTIR spectroscopy. The focus of interest was the effect of the iodide anion on the important vibrational bands of acetonitrile. The main effect of the LiI electrolyte is to shift the C≡N stretching frequency in the blue direction due to interaction of the Li + cation with the electronegative C≡N group. However, a small red shift of the C≡N stretching mode due to the interaction of I - with the methyl group of acetonitrile is found in both electrolytes. On the other hand, the symmetic and asymmetric stretching modes of the methyl group are significantly red shifted in the presence of LiI. Ab initio quantum chemical calculations were carried out to determine the optimum location of the Li + and I - ions in ion-solvent complexes containing a varying number of solvent molecules. These calculations correctly predict the direction of the observed shifts for all the principal bands of acetonitrile except the methyl stretching modes.",
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AU - Pálinkás, G.

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N2 - The vibrational spectra of acetonitrile solutions containing lithium iodide and tetrabutylammonium iodide have been studied using ATR-FTIR spectroscopy. The focus of interest was the effect of the iodide anion on the important vibrational bands of acetonitrile. The main effect of the LiI electrolyte is to shift the C≡N stretching frequency in the blue direction due to interaction of the Li + cation with the electronegative C≡N group. However, a small red shift of the C≡N stretching mode due to the interaction of I - with the methyl group of acetonitrile is found in both electrolytes. On the other hand, the symmetic and asymmetric stretching modes of the methyl group are significantly red shifted in the presence of LiI. Ab initio quantum chemical calculations were carried out to determine the optimum location of the Li + and I - ions in ion-solvent complexes containing a varying number of solvent molecules. These calculations correctly predict the direction of the observed shifts for all the principal bands of acetonitrile except the methyl stretching modes.

AB - The vibrational spectra of acetonitrile solutions containing lithium iodide and tetrabutylammonium iodide have been studied using ATR-FTIR spectroscopy. The focus of interest was the effect of the iodide anion on the important vibrational bands of acetonitrile. The main effect of the LiI electrolyte is to shift the C≡N stretching frequency in the blue direction due to interaction of the Li + cation with the electronegative C≡N group. However, a small red shift of the C≡N stretching mode due to the interaction of I - with the methyl group of acetonitrile is found in both electrolytes. On the other hand, the symmetic and asymmetric stretching modes of the methyl group are significantly red shifted in the presence of LiI. Ab initio quantum chemical calculations were carried out to determine the optimum location of the Li + and I - ions in ion-solvent complexes containing a varying number of solvent molecules. These calculations correctly predict the direction of the observed shifts for all the principal bands of acetonitrile except the methyl stretching modes.

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