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Gas phase RDX decomposition pathways using coupled cluster theory

Molt, Robert, Watson, Thomas, Bazanté, Alexandre P., Bartlett, Rodney J. and Richards, Nigel G.J. 2016. Gas phase RDX decomposition pathways using coupled cluster theory. Physical Chemistry Chemical Physics 18 (37) , pp. 26069-26077. 10.1039/C6CP05121A

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Abstract

Electronic and free energy barriers for a series of gas-phase RDX decomposition mechanisms have been obtain using coupled cluster singles, doubles, and perturbative triples with complete basis set (CCSD(T)/CBS) electronic energies for MBPT(2)/cc-pVTZ structures. Importantly, we have located a well-defined transition state for NN homolysis, in the initial RDX decomposition step, thereby obtaining a true barrier for this reaction. These calculations support the view that HONO elimination is preferred at STP over other proposed mechanisms, including NN homolysis, “triple whammy” and NONO isomerization. Indeed, our calculated values of Arrhenius parameters are in agreement with experimental findings for gas phase RDX decomposition. We also investigate a number of new pathways leading to breakdown of the intermediate formed by the initial HONO elimination, and find that NN homolysis in this intermediate has an activation energy barrier comparable with that computed for HONO elimination.

Item Type: Article
Date Type: Published Online
Status: Published
Schools: Chemistry
Subjects: Q Science > QD Chemistry
Publisher: Royal Society of Chemistry
ISSN: 1463-9076
Date of First Compliant Deposit: 26 October 2016
Date of Acceptance: 25 August 2016
Last Modified: 06 Sep 2017 10:48
URI: http://orca.cf.ac.uk/id/eprint/95604

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