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Kinetic shifts and metastable transitions
Author(s) -
Hickling R. D.,
Jennings K. R.
Publication year - 1970
Publication title -
organic mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 0030-493X
DOI - 10.1002/oms.1210031206
Subject(s) - metastability , kinetic energy , ion , spectral line , atomic physics , chemistry , fragment (logic) , intensity (physics) , physics , optics , organic chemistry , astronomy , computer science , programming language , quantum mechanics
Differences in the appearance potentials of normal fragment ions and of metastable transitions leading to the formation of the same fragment ions have been measured in the mass spectra of a number of compounds. The differences varied from 0.1 to 1.0 eV and were attributed to the measurable part of the kinetic shift. An approximate correlation was found between the intensity of a ‘metastable peak’ and the observed difference in appearance potentials, and it is suggested that the full kinetic shift for processes giving rise to intense ‘metastable peaks’ is substantially larger than the measurable part. The implications of this in thermochemical calculations are discussed.