Abstract
Electron capture negative ion (ECNI) mass spectrometry is a technique used to detect trace levels of electrophilic compounds in complex matrices. ECNI mass spectra can also provide information regarding molecular structure. In this paper, current knowledge regarding the modes of negative ion formation under ECNI conditions is presented. Types of negative ions that have been observed in ECNI mass spectra are summarized based upon spectra that have appeared in the literature and upon the spectra of over 350 compounds that were measured in our laboratory. Factors that influence molecular ion stability and sensitivity to isomeric structures are addressed.
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