E. Uggerud, Translational energy release: Experiment and theory. H-2 elimination reactions of small gas phase ions, and correspondence to H-H bond activation, MASS SPECTR, 18(5), 1999, pp. 285-308
All unimolecular decompositions are accompanied by a specific translational
energy release. Translational energy release distributions can be precisel
y measured with a magnetic sector mass spectrometer The experimental method
s used for this purpose are described. The precise amount of translational
energy released in the common centre of mass formed in a fragmentation reac
tion is a direct outcome of the detailed reaction dynamics of the system. I
t is described how recent development in reaction trajectory calculations w
ith ab initio quantum chemical potential energy functions call be used to c
alculate translational energy release. The shape of a potential energy surf
ace, and in particular the barrier height, are important for how much energ
y is released In this review a much studied reaction type, H-2 eliminations
is reviewed. The reviewer has carefully examined the individual reactions
in order to reveal the electronic factors that determine the shape of the p
otential energy profile. It turns out that frontier orbital theory provides
a simple and solid theoretical framework. (C) 1999 John Wiley & Sons, Inc.
, Mass Spec Rev 18: 285-308, 1999.