Journal of the American Chemical Society, Vol.118, No.43, 10640-10644, 1996
Unimolecular Reaction-Kinetics in the High-Pressure Limit Without Collisions
Molecular activation by blackbody photons, first postulated in 1919 by Perrin, plays a dominant role in the unimolecular dissociation of large ions trapped at low pressure in a Fourier-transform mass spectrometer. Under readily achievable experimental conditions, molecular ions of the protein ubiquitin equilibrate with the blackbody radiation field inside the vacuum chamber. The internal energy of a population of these ions is given by a Boltzmann distribution. From the temperature dependence of unimolecular dissociation rate constants measured in the zero-pressure limit, Arrhenius activation parameters equal to those in the high-pressure limit are obtained.
Keywords:TANDEM MASS-SPECTROMETRY;MULTIPLY-CHARGED IONS;SMALL CLUSTER IONS;GAS-PHASE;ELECTROSPRAY-IONIZATION;CYTOCHROME-C;DIELECTRIC POLARIZABILITY;DISSOCIATION;PROTEINS;OLIGONUCLEOTIDES