Assigning Structures to Ions in Mass Spectrometry by Paul M. Mayer, Christiane Aubry, John Holmes

By Paul M. Mayer, Christiane Aubry, John Holmes

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In general this assumption may not be correct. Traeger88 emphasized this problem in 1982 and in all his photon-induced AE measurements assumes that the products are at 0 K and is careful in the identification of the true onset for the ion signal. 7b to include the energy required to raise the products from 0 K to 298 K. In the authors’ view, this is likely an overcorrection because 0 K products would only result from a situation of low probability where, in the transition state for the observed limiting rate constant, all of the internal (rotational and vibrational) energy of ABþ is located in the reaction coordinate.

For many ion dissociations, the identity of the fragment ion, at least provisionally, can be assumed on the basis of chemical common sense. However, because the rearrangement of a precursor molecular ion that leads to the transition state of lowest AE can often be profoundly complex, the structures of the dissociation products may turn out to be very different from those predicted and based on intuition alone and therefore cannot be taken for granted. If the reaction that produces the desired ion is simple enough, then the structure of the neutral product will not be in doubt because small molecules and radicals have no isomers.

The resulting frequency spectrum is converted to a mass spectrum by applying a calibration. The main uses of the FT-ICR method, besides its capacity for ultrahigh mass resolution (as high as 106), have been the study of ion–molecule reaction kinetics and mechanisms and especially the analysis of large biomolecules. The reader is particularly directed to the journal Mass Spectrometry Reviews, where many articles about the specialized uses of FT-ICR MS can be found. Time-of-Flight Mass Spectrometers This method for separating ions is perhaps the simplest of all and was among the earliest of mass spectrometers.

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