By applying different electric field strengths to the orifice-skimmer regio
n of an electrospray ionization mass spectrometer, the rate of dissociation
can be varied based on the amount of infernal energy acquired by an ion th
rough collisions: with the curtain gas molecules. Both the Arrhenius equati
on and Rice-Ramsperger-Kassel (RRK) theory can be used to predict the rate
of dissociation of internally excited molecules. A previously determined mo
del for collision-induced dissociation is tested by comparison of predicted
and experimentally observed orifice-skimmer potential differences for diss
ociation of ions. The rate of collision-induced dissociation of bradykinin
ions is determined by monitoring the fragments produced in a mass spectrome
ter. The semi-quantitative model is found to yield effective predictions wh
en accurate Arrhenius and RRK parameters are utilized. (C) 2001 American So
ciety for Mass Spectrometry.