Product energy and angular momentum partitioning in the unimolecular dissociation of aluminum clusters

Gilles H. Peslherbe, William L. Hase

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25 Scopus citations

Abstract

A previous classical trajectory simulation showed that the unimolecular decompositions of Al6 and Al13 are intrinsically RRKM. In the work presented here, this study is further analyzed to determine the Al5 + Al and Al12 + Al product energy distributions, which are compared with the predictions of statistical theories. Orbiting transition state/phase space theory (OTS/PST) gives distributions in excellent agreement with the trajectory results. Assuming a loose, product-like transition state gives a lower average product translational energy, 〈Et〉, than what is found with the orbiting transition state. Including anharmonicity, in the calculation of the product vibrational density of states, increases the energy partitioned to product vibration. The Engelking model for cluster decomposition overestimates 〈Et〉. One Klots model gives an inaccurate 〈Et〉, but a second model more firmly rooted in phase space theory performs quite well. The Engelking model, for deducing the cluster dissociation energy from the measured 〈Et〉, does not give accurate results for Al6 and Al13 dissociation.

Original languageEnglish
Pages (from-to)10556-10564
Number of pages9
JournalJournal of Physical Chemistry A
Volume104
Issue number45
DOIs
StatePublished - Nov 16 2000

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