Determination of positions, velocities, and kinetic energies of resonantly excited ions in the quadrupole ion trap mass spectrometer by laser photodissociation.

The effects on ion motion caused by the application of a resonance AC dipole voltage to the end-cap electrodes of the quadrupole ion trap are described. An excimer laser is used to photodissociate benzoyl ions, and its triggering is phase locked to the AC voltage to follow the motion of the ion cloud as a function of the phase angle of the AC signal. Resonantly excited ions maintain a coherent motion in the presence of He buffer gas, which dissipates energy from the ions via collisions. Maximum ion displacements, which depend upon the potential well depth (q z value), occur twice each AC cycle. Axial components of ion velocities are determined by differentiating the displacements of the distributions with respect to time. The experimental data show that these velocities are maximized when the ion cloud passes through zero axial displacement, and they compare favorably with results calculated using a simple harmonic oscillator model. Axial components of ion kinetic energies are low (<5 eV) under the chosen experimental conditions. At low values of q2 (≈ 0.2), the width of the ion distribution increases as the ion cloud approaches the center of the trap and decreases as it approaches the end-cap electrodes. This effect is created by compaction of the ion trajectories when ion velocities are decreased.

High resolution on a quadrupole ion trap mass spectrometer.

By using a modified ion trap mass spectrometer, resolution in excess of 30,000 (FWHM) at m I z 502 is demonstrated. The method of increasing resolution in the ion trap mass spectrometer operated in the mass-selective instability mode depends on decreasing the rate of scanning the primary radio frequency amplitude as well as using resonance ejection at the appropriate frequency and amplitude. A theoretical basis for the method is introduced.