Anion photoelectron spectroscopy of acetonitrile cluster anions, (CH3CN)(-)(n) (n=10-100), successfully demonstrates the competitive coexistence of two different anionic species: a solvated electron and a solvent-bound valence anion. The distinctly different nature of these anions is revealed by hole-burning-type photoelectron spectroscopy and relative photodetachment cross section measurements. This unusual coexistence is attributed to the closely lying nature of their anionic states at just the number of solvent molecules sufficient to almost complete the first solvation layer.
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