Theory and application of dissociative electron capture in molecular identification.
The coupling of an electron monochromator (EM) to a mass spectrometer (MS) has created a new analytical technique, EM-MS, for the investigation of electrophilic compounds. This method provides a powerful tool for molecular identification of compounds contained in complex matrices, such as environmental samples. In particular, EM-MS has been applied to the detection of nitrated aromatic compounds, many of which are potent mutagens and/or carcinogens and are considered environmental hazards. EM-MS expands the application and selectivity of traditional MS through the inclusion of a new dimension in the space of molecular characteristics-the electron resonance energy spectrum. EM-MS also enhances detection sensitivity as well because the entire electron flux of the proper energy can be delivered into the negative ion resonance that is analytically most useful to solving the problem at hand. However, before this tool can realize its full potential, it will be necessary to create a library of resonance energy scans from standards of the molecules for which EM-MS offers a practical means of detection. Unfortunately, the number of such standards is very large and not all of the compounds are commercially available, making this library difficult to construct. Here, an approach supplementing direct measurement with chemical inference and quantum scattering theory is presented to demonstrate the feasibility of directly calculating resonance energy spectra. This approach makes use of the symmetry of the transition-matrix element of the captured electron to discriminate between the spectra of isomers. As a way of validating this approach, the resonance values for 25 nitrated aromatic compounds were measured along with their relative abundance. Subsequently, the spectra for the isomers of nitrotoluene were shown to be consistent with the symmetry-based model. The initial success of this treatment suggests that it might be possible to predict negative ion resonances and thus create a library of EM-MS standards.