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Eur. J. Mass Spectrom. 8, 85 - 98 (2002)

Kinetic shifts

C. Lifshitz
Department of Physical Chemistry and The Farkas Center for Light Induced Processes, The Hebrew University of Jerusalem, Jerusalem 91904, Israel

ABSTRACT:
The kinetic shift is the excess energy required to observe detectable dissociation within a certain experimental time frame. Kinetic shifts are of central importance when energetic attributes are deduced from appearance energy measurements. Their importance has become of renewed interest since larger molecules are being studied mass spectrometrically. This is a review paper on the topic of kinetic shifts. It is made up of the following sections: Introduction, Definitions, Experimental methods, Statistical theories, Examples: Aromatic and polycyclic aromatic hydrocarbons, fullerenes, metal cationwater, alcohol and ether complexes, Conclusions.

Keywords: conventional, intrinsic and competitive kinetic shifts, appearance energies, ion traps, PEPICO, TRPD, CID, RRKM/QET, FHBT, PIE, microcanonical rate constants, breakdown curves, radiative decay, FT-ICR, CIT-RETOF

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