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The internal energy of product ions formed in mass spectral reactions
Author(s) -
McAdoo D. J.,
Bente P. F.,
Gross M. L.,
McLafferty F. W.
Publication year - 1974
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.1210090510
Subject(s) - internal energy , ion , product (mathematics) , energy (signal processing) , chemistry , thermodynamics , chemical physics , atomic physics , physics , organic chemistry , mathematics , geometry , quantum mechanics
Major factors which determine the distribution of internal energy of a primary product ion A + , P ( E ) A+ , at formation are delineated in terms of the quasi‐equilibrium theory and a variety of experimental evidence is offered to support these conclusions. These major factors include: the P ( E ) of the molecular ion, the rate constants as a function of energy, κ( E ), for M + ·→A + + N 0 and for competing reactions of M + ·, and the partitioning of excess internal energy between A + and N 0 . The ‘fluctuation effect’ on this partitioning makes P ( E ) A+ relatively insensitive to many structural and energy changes.