Activation of Peptide ions by blackbody radiation: factors that lead to dissociation kinetics in the rapid energy exchange limit.

Unimolecular rate constants for blackbody infrared radiative dissociation (BIRD) were calculated for the model protonated peptide (AlaGly)(n) (n = 2-32) using a variety of dissociation parameters. Combinations of dissociation threshold energies ranging from 0.8 to 1.7 eV and transition entropies corresponding to Arrhenius preexponential factors ranging from very "tight" (A(infinity) = 10(9.9) s(-1)) to "loose" (A(infinity) = 10(16.8) s(-1)) were selected to represent dissociation parameters within the experimental temperature range (300-520 K) and kinetic window (k(uni) = 0.001-0.20 s(-1)) typically used in the BIRD experiment. Arrhenius parameters were determined from the temperature dependence of these values and compared to those in the rapid energy exchange (REX) limit. In this limit, the internal energy of a population of ions is given by a Boltzmann distribution, and kinetics are the same as those in the traditional high-pressure limit. For a dissociation process to be in this limit, the rate of photon exchange between an ion and the vacuum chamber walls must be significantly greater than the dissociation rate. Kinetics rapidly approach the REX limit either as the molecular size or threshold dissociation energy increases or as the transition-state entropy or experimental temperature decreases. Under typical experimental conditions, peptide ions larger than 1.6 kDa should be in the REX limit. Smaller ions may also be in the REX limit depending on the value of the threshold dissociation energy and transition-state entropy. Either modeling or information about the dissociation mechanism must be known in order to confirm REX limit kinetics for these smaller ions. Three principal factors that lead to the size dependence of REX limit kinetics are identified. With increasing molecular size, rates of radiative absorption and emission increase, internal energy distributions become relatively narrower, and the microcanonical dissociation rate constants increase more slowly over the energy distribution of ions. Guidelines established here should make BIRD an even more reliable method to obtain information about dissociation energetics and mechanisms for intermediate size molecules.