The coupling between ambient ionization sources, developed for mass spectrometric analysis of biomolecules, and cryogenic ion processing, originally designed to study interstellar chemistry, creates a new and general way to capture transient chemical species and elucidate their structures with optical spectroscopies.  Advances in non-linear optics over the past decade allow single-investigator, table top lasers to access radiation from 550 cm^-1 in the infrared to the vacuum ultraviolet.