In
contrast to classical ion mobility spectrometers (IMS) operating
at ambient pressure, the high kinetic energy ion mobility spectrometer
(HiKE-IMS) is operated at reduced pressures between 10–40 mbar.
In HiKE-IMS, ions are generated in a reaction region before they are
separated in a drift region. Due to the operation at reduced pressure,
it is possible to reach high reduced electric field strengths up to
120 Td in both the reaction as well as drift region, resulting in
a pronounced decrease in chemical cross sensitivities and a significant
enhancement of the dynamic range. Until now though, only limited knowledge
about the ionization pathways in HiKE-IMS is available. Typically,
proton bound water clusters, H+(H2O)
n
, are the most abundant positive reactant ion species
in classical IMS with atmospheric chemical ionization sources. However,
at reduced pressure and increased effective ion temperature, the reactant
ion population significantly changes. As the ionization efficiency
of analyte molecules in HiKE-IMS strongly depends on the reactant
ion population, a detailed knowledge of the reactant ion population
generated in HiKE-IMS is essential. Here, we present a coupling stage
of the HiKE-IMS to a mass spectrometer enabling the identification
of ion species and the investigation of ion molecule reactions prevailing
in HiKE-IMS. In the present study, the HiKE-IMS–MS is used
to identify positive reactant ion populations in both, purified air
and nitrogen, respectively. The experimental data suggest the generation
of systems of clustered primary ions (H+(H2O)
n
, NO+(H2O)
m
, and O2
+(H2O)
p
), which most probably serve as reactant
ions. Their relative abundances highly depend on the reduced electric
field strength in the reaction region. Furthermore, their effective
mobilities are studied as a function of the reduced electric field
strength in the drift region.