The C=O stretching [(C=O)] Raman bands of the carbonyl solvents, S (acetone and acetophenone), in some electrolytic solutions of lithium and sodium salts (M+X) are analyzed. The large and negative values of the noncoincidence effect ( ) measured for the component of this band generated by the solvent–ion interactions are interpreted in the light of the results of ab initio quantum chemical calculations performed for clusters of type (S)nM+, and also on the basis of the transition dipole coupling (TDC) mechanism between pairs of (C=O) oscillators. The effects of the size of the ion M+ and of the solvation number n on the NCE are analyzed. It is shown that the decrease of the NCE resulting from the change in the size of the ion M+ from Li+ to Na+ is appreciably counterbalanced by the increase of the NCE arising form the change in the ion solvation number n from 4 for Li+ to 6 for Na+.

Influence of ions on the structural organization of the polar liquids probed by the noncoincidence effect. Experimental and quantum chemical results.

GIORGINI, MARIA GRAZIA;
2008

Abstract

The C=O stretching [(C=O)] Raman bands of the carbonyl solvents, S (acetone and acetophenone), in some electrolytic solutions of lithium and sodium salts (M+X) are analyzed. The large and negative values of the noncoincidence effect ( ) measured for the component of this band generated by the solvent–ion interactions are interpreted in the light of the results of ab initio quantum chemical calculations performed for clusters of type (S)nM+, and also on the basis of the transition dipole coupling (TDC) mechanism between pairs of (C=O) oscillators. The effects of the size of the ion M+ and of the solvation number n on the NCE are analyzed. It is shown that the decrease of the NCE resulting from the change in the size of the ion M+ from Li+ to Na+ is appreciably counterbalanced by the increase of the NCE arising form the change in the ion solvation number n from 4 for Li+ to 6 for Na+.
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11585/63006
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