A High Kinetic Energy Ion Mobility Spectrometer for Operation at Higher Pressures of up to 60 mbar

J Am Soc Mass Spectrom. 2023 May 3;34(5):893-904. doi: 10.1021/jasms.2c00365. Epub 2023 Mar 31.

Abstract

High Kinetic Energy Ion Mobility Spectrometers (HiKE-IMS) are usually operated at absolute pressures around 20 mbar in order to reach high reduced electric field strengths of up to 120 Td for influencing reaction kinetics in the reaction region. Such operating points significantly increase the linear range and limit chemical cross sensitivities. Furthermore, HiKE-IMS enables ionization of compounds normally not detectable in ambient pressure IMS, such as benzene, due to additional reaction pathways and fewer clustering reactions. However, operation at higher pressures promises increased sensitivity and smaller instrument size. In this work, we therefore study the theoretical requirements to prevent dielectric breakdown while maintaining high reduced electric field strengths at higher pressures. Furthermore, we experimentally investigate influences of the pressure, discharge currents and applied voltages on the corona ionization source. Based on these results, we present a HiKE-IMS that operates at a pressure of 60 mbar and reduced electric field strengths of up to 105 Td. The corona experiments show shark fin shaped curves for the total charge at the detector with a distinct optimum operating point in the glow discharge region at a corona discharge current of 5 μA. Here, the available charge is maximized while the generation of less-reactive ion species like NOx+ is minimized. With these settings, the reactant ion population, H3O+ and O2+, for ionizing and detecting nonpolar substances like n-hexane is still available even at 60 mbar, achieving a limit of detection of just 5 ppbV for n-hexane.