Application of laser photofragmentation-resonance enhanced multiphoton ionization to ion mobility spectrometry

We demonstrate detection of nitro-containing compounds with laser photofragmentation (PF) coupled with resonance enhanced multiphoton ionization (REMPI) and ion mobility spectrometry (IMS). In PF-REMPI, a laser dissociates the parent molecules, producing fragments that can then be ionized by absorption of additional laser photons. The production of these ions strongly depends on the wavelength of laser light, with ion yields corresponding to the absorption spectrum of the fragments [nitric oxide (NO) in the present case]. Combining IMS with PF-REMPI provides further specificity, separating ions according to their mobilities through an atmospheric-pressure drift tube. In this work, we use a pulsed UV laser to examine the characteristics of atmospheric-pressure PF-REMPI, the chemistry occurring in the ionization region and drift tube, and the viability of detecting ions created by both resonance-enhanced and nonresonant ionization. Probing NO in a helium-nitrogen bath, we demonstrate that the detection of ions displays single-shot response to changes in ion generation, with an ion extraction-to-collection efficiency of approximately 12%. We then evaluate the sensitivity and specificity of PF-REMPI/IMS as applied to the detection of both the explosive surrogate 2, 4-dinitrotoluene and the nuisance compound nitrobenzene.