Abstract
The unimolecular decomposition of large polyatomic hydrocarbon (120 and 1000 modes) and protein (540 modes) molecules and molecular ions is investigated by applying RRKM, effective RRK (ERRK), and Arrhenius models. It is found that the calculated values of the RRKM unimolecular rate coefficients, k(E), agree well with fragmentation lifetimes of molecular ions in a mass spectrometer. Calculations of the effective number of modes at a given temperature and excitation energy together with ERRK expression for k(E) yield values which are similar to those calculated by RRKM
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