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Title: Thermal decomposition of 1,3,3-trinitroazetidine (TNAZ): A density functional theory and ab initio study

Density functional theory and ab initio methods are employed to investigate decomposition pathways of 1,3,3-trinitroazetidine initiated by unimolecular loss of NO{sub 2} or HONO. Geometry optimizations are performed using M06/cc-pVTZ and coupled-cluster (CC) theory with single, double, and perturbative triple excitations, CCSD(T), is used to calculate accurate single-point energies for those geometries. The CCSD(T)/cc-pVTZ energies for NO{sub 2} elimination by N–N and C–N bond fission are, including zero-point energy (ZPE) corrections, 43.21 kcal/mol and 50.46 kcal/mol, respectively. The decomposition initiated by trans-HONO elimination can occur by a concerted H-atom and nitramine NO{sub 2} group elimination or by a concerted H-atom and nitroalkyl NO{sub 2} group elimination via barriers (at the CCSD(T)/cc-pVTZ level with ZPE corrections) of 47.00 kcal/mol and 48.27 kcal/mol, respectively. Thus, at the CCSD(T)/cc-pVTZ level, the ordering of these four decomposition steps from energetically most favored to least favored is: NO{sub 2} elimination by N–N bond fission, HONO elimination involving the nitramine NO{sub 2} group, HONO elimination involving a nitroalkyl NO{sub 2} group, and finally NO{sub 2} elimination by C–N bond fission.
Authors:
;  [1]
  1. Department of Chemistry, University of Missouri-Columbia, Columbia, Missouri 65211 (United States)
Publication Date:
OSTI Identifier:
22253113
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 140; Journal Issue: 15; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; DENSITY FUNCTIONAL METHOD; FISSION; NITROGEN DIOXIDE; PYROLYSIS