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Keywords:

  • collision-induced dissociation;
  • collisional energy transfer;
  • mechanisms of collisional excititation;
  • tandem mass spectrometry;
  • curve-crossing excitation;
  • impulsive collisions;
  • slow-heating methods;
  • surface-induced dissociation

Abstract

This article is a review of the mechanisms responsible for collisional activation of ions in mass spectrometers. Part I gives a general introduction to the processes occurring when a projectile ion and neutral target collide. The theoretical background to the physical phenomena of curve-crossing excitation (for electronic and vibrational excitation), impulsive collisions (for direct translational to vibrational energy transfer), and the formation of long-lived collision intermediates is presented. Part II highlights the experimental and computational investigations that have been made into collisional activation for four experimental conditions: high (>100 eV) and intermediate (1–100 eV) center-of-mass collision energies, slow heating collisions (multiple low-energy collisions) and collisions with surfaces. The emphasis in this section is on the derived post-collision internal energy distributions that have been found to be typical for projectile ions undergoing collisions in these regimes. © 2009 Wiley Periodicals, Inc., Mass Spec Rev 28:608–639, 2009