The quadrupole ion trap mass spectrometer is of great interest for che
mical analysis. Nevertheless, negative ion studies using in situ ioniz
ation (negative ions created inside the ion trap) are difficult and li
mited. This paper describes the difficulties that occurred during nega
tive ion analysis when using a commercial gas chromatography quadrupol
e ion trap mass spectrometer (GC/MS) system. Detection problems, due t
o simultaneous trapping of both positive and negative ions, are explai
ned by the large kinetic energies of the ejected ions. Negative ion fo
rmation, produced by electron capture, is limited by the fundamental R
F field, which imparts high kinetic energy to the electrons, precludin
g the possibility that the electrons will reach the thermal energies n
eeded for electron capture processes. In addition, simultaneous confin
ement of negative and positive ions affects the recorded mass spectra.
Space charge potentials that exist inside the ion trap (due to the io
nization conditions necessary to detect negative ions) induce the dest
abilization of positive ions at higher mit ratios, while negative ions
in the same mit range are stabilized. Moreover, loss of resolution an
d decalibration could occur for negative ions when they are ejected in
the presence of positive ions with higher mit ratios. At the very lea
st, ion-ion reactions could limit the observation of negative ions. Th
e understanding of these phenomena, viz. detection, formation, and sim
ultaneous confinement, will permit the proposal of solutions for negat
ive ion analysis with quadrupole ion trap mass spectrometers using in
situ ionization.