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Note that at a storage level of 48 m/z and a CID bandwidth of 4 kHz, the mass
range increases from 3 to 40 m/z when the parent ion mass increases from 100
to 400 m/z. Given a parent ion mass of 400 m/z and a CID bandwidth of 4 kHz,
the mass range decreases from 40 m/z for a storage level of 48 m/z to a range of
12 m/z for a storage level of 143 m/z.
The amount of energy that is converted to internal energy in the parent ion
depends on the number of collisions (excitation time), the relative energy of the
collisions (CID excitation amplitude), and the rate that the internal energy is
removed by collisional deactivation (excitation method). Collision-induced
dissociation in the ion trap is always in competition with ion ejection. If the CID
excitation amplitude selected is too large, the parent ion will be ejected to the
trap electrodes before it can collide with background helium atoms. If the CID
excitation amplitude selected is too small, the energy of the parent ion will not
exceed the internal energy threshold required to break the chemical bonds and
form product ions. This is because energy is constantly being removed by low
energy collisional deactivation. Therefore, the CID excitation amplitude and the
excitation time are both used to optimize the CID process in conjunction with an
appropriate choice of excitation method.
Product Ion Mass Scanning
Following formation of the product ions by collision-induced dissociation, a single
rf ramp is used along with the axial modulation field to resonantly scan ions from
the trap into the electron multiplier. This process generates the product ion
spectrum.
Chemical Ionization
Chemical ionization (CI) may also be used to selectively fill the ion trap. In this
case, the ion formation and matrix ion ejection steps described above are
modified. Insertion of the three subsequent MS/MS operations, i.e., parent ion
isolation, product ion formation, and product ion mass scanning, into the basic CI
scan function (following the ionization and reaction steps) creates the CI-MS/MS
scan function.
EI/MS/MS and CI/MS/MS Automatic Space Charge
Control
Space charge control for EI/MS/MS and CI/MS/MS occurs by forming the ions
during a fixed ionization period. Ion formation occurs in the same manner as for
EI or CI. After ion formation, all ions outside of the isolation window specified by
the user are removed from the trap. The ions are subsequently scanned from the
trap at the normal scan rate.
Summary
The four operations described above, i.e., ionization, parent ion isolation, product
ion formation, and product ion mass scanning, are used in the analytical scan.
When automatic space charge control is used the number of parent ions in the
isolation window are used to determine the ionization time required to maintain
the optimum number of ions in the trap. Thus, the total ion space charge level is
held constant as the sample and matrix levels change. Maintaining a constant
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