Collisional activation of ions by off-resonance irradiation in ion cyclotron resonance spectrometry

Collisional activation of ions in the ion cyclotron resonance (ICR) cell by short off-resonance burst irradiation (ORBI) was studied by time-resolved photodissociation of the meta-bromotoluene radical cation. Off-resonance chirp or single-frequency burst was applied for 2 ms to the probe ion in the presence of At buffer gas. The amount of internal energy imparted to the probe ion by collision under ORBI was precisely determined by time-resolved photodissociation spectroscopy. The rate of unimolecular dissociation of the probe ion following the photolysis at 532 nm was measured by monitoring the real-time appearance of the C(7)H(7)(+) product ion. The internal energy of the probe ion was extracted from the known rate-energy curve. To help understand the collisional activation of an ion under ORBI, we simulated the radial trajectory of the ion using Green's method. The calculated radial kinetic energy was converted to the collision energy in the center-of-mass frame, and the collision frequency was estimated by using a reactive hard-sphere collision model with an ion-induced dipole potential. Both experiments and trajectory simulations suggest that chirp irradiation leads to less collisional activation of ions than other waveforms. (C) 2009 Elsevier B.V. All rights reserved.X1111sciescopu