Abstract
The competitive solvation of the sodium ion by acetone and methanol has been investigated by vibrational spectroscopy of the C–O and O–H stretching modes of methanol and by unimolecular dissociation of mass-selected cluster ions using a tandem mass spectrometer. The onset of hydrogen bonding was detected by substantial shifts in the C–O (+12 to +16 cm−1) and O–H (−200 cm−1) stretches, as well as by significant increases in the intensity and width of the O–H bands. These onsets were observed when a total of five molecules were present about the ion. The unimolecular dissociation rates of metastable ion clusters of composition Na+((CH3)2CO)1–9 and Na+((CH3)2CO)1–8(CH3OH)1 were also measured using the same experimental apparatus. A significant increase in rate was observed when seven or more acetone molecules were present, suggesting a solvent shell size of six.
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