Ion Dissociation Kinetics in Mass Spectrometry

Unimolecular rate constant; microcanonical rate constant; canonical rate constant; kinetic isotope effects; reaction mechanisms; non-adiabatic processes; tunneling; isolated state decay; transition state theory; RRKM theory; kinetic energy release

Abstract :

[en] The variation of fragmentation rate constants as a function of the parent ion internal energy, or, alternatively, as a function of temperature, is crucial information to unravel the dissociation mechanisms of molecular ions. This contribution provides the reader first with basic information on the statistical theories used to model unimolecular rate constants. Various experimental methods to measure such rate constants in the 102 to 1010 s^(-1) range are then discussed. Kinetic isotope effects are also briefly dealt with. How reaction mechanisms can be inferred from kinetic data is handled in an extensive section where selected examples from the recent literature are discussed.

Research Center/Unit :

Department of Chemistry, University of Liège

Disciplines :

Chemistry

Author, co-author :

Leyh, Bernard ; Université de Liège - ULiège > Département de chimie (sciences) > Laboratoire de dynamique moléculaire

Language :

English

Title :

Ion Dissociation Kinetics in Mass Spectrometry

Alternative titles :

[fr] Cinétique des dissociations ioniques en spectrométrie de masse

Publication date :

2013

Main work title :

Reference Module in Chemistry, Molecular Sciences and Chemical Engineering

Editor :

Reedijk, J.

Publisher :

Elsevier, Waltham, United States - Massachusetts

Peer reviewed :

Peer reviewed

Additional URL :

http://www.sciencedirect.com/science/referenceworks/9780124095472

Funders :

ULiège - Université de Liège

Available on ORBi :

since 21 October 2013

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