A model for ionization mechanisms in field desorption mass spectrometry.

The apparent discrepancy between theory and experimental practices in field desorption mass spectrometry has encouraged a study attempting to focus theoretical concepts more clearly into forms recognizable to the chemical investigator. Preliminary results indicate that best anode temperature for many compounds is independent of the applied voltage throughout the range available on the Varian MAT CH-5 double focusing mass spectrometer with the electron impact-field ionization-field desorption combined source. Studies of mass transfer indicate that desorption of the sample at the best anode temperature occurs in the absence of the applied field and at a rate which is indistinguishable from the rate of desorption in the presence of the field. These results and other observations, have led us to postulate a new mechanism of ion formation, involving chemical attachment reactions in a thin fluidized system. Clearly, the role of the field in this technique must be the subject of continued study.