A new approach to IRMPD using selective ion dissociation in a quadrupole ion trap.

Infrared multiphoton photodissociation (IRMPD) in a quadrupole ion trap is not selective for a parent ion. Product ions are decreased in abundance by continuous sequential dissociation and may be lost below the low mass cut-off. The IRMPD process is made selective by resonantly exciting trapped ions into an axially offset laser path. Product ions form and collisionally relax out of the laser path to accumulate in the center of the trap. The technique, termed selective broadband (SB) IRMPD, limits sequential dissociation to preserve first generation product ion abundance. The abundances of larger product ions are maximized by completely dissociating the parent ion, but continuous sequential dissociation does not form small product ions below the low mass cut-off associated with conventional IRMPD. Smaller product ions are further increased in abundance in another tandem mass spectrum by performing sequential stages of SB-IRMPD, adjusting the trapping rf amplitude to dissociate larger product ions at the same q(z) range. Thermal assistance is used to perform SB-IRMPD at higher bath gas pressures for increased sensitivity.