The trapping of neutral and electrically charged molecular reaction intermediates in the solid rare gases and the characterization of these intermediates by vibrational and electronic spectroscopy are surveyed. Spectral data for reaction intermediates trapped in solid neon and argon are compared with the corresponding data obtained from gas phase studies and from quantum chemical calculations. Emphasis is placed on recent progress, including the production, stabilization, and spectroscopic study of highly reactive small molecular ions and the use of ab initio and density functional calculations for the identification of reaction intermediates.
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