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| Title
| - Influence of Ions on the Structural Organization of Dipolar Liquids Probed by the Noncoincidence Effect: Experimental and Quantum Chemical Results
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| Abstract
| - The CO stretching [ν(CO)] 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 (NCE = ν̃ani − ν̃iso) 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 mechanism between pairs of ν(CO) 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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| - Structural Organization of Dipolar Liquids Probed by the NCE
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