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The Mechanism for Unimolecular Decomposition of RDX (1,3,5-Trinitro-1,3,5-triazine), an ab Initio Study

Chakraborty, Debashis and Muller, Richard P. and Dasgupta, Siddharth and Goddard, William A., III (2000) The Mechanism for Unimolecular Decomposition of RDX (1,3,5-Trinitro-1,3,5-triazine), an ab Initio Study. Journal of Physical Chemistry A, 104 (11). pp. 2261-2272. ISSN 1089-5639. https://resolver.caltech.edu/CaltechAUTHORS:20170719-134437924

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Abstract

Gas phase hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) is a relatively stable molecule which releases a large amount of energy upon decomposition. Although gas-phase unimolecular decomposition experiments suggest at least two major pathways, there is no mechanistic understanding of the reactions involving RDX or other energetic molecules (such as HMX and TATB), used in applications ranging from automobile air bags to rocket propellants. For the unimolecular decomposition of RDX, we find three pathways:  (i) concerted decomposition of the ring to form three CH_2NNO_2 (M = 74) molecules, and (ii) homolytic cleavage of an NN bond to form NO_2 (M = 46) plus RDR (M = 176), which subsequently decomposes to form various products. Experimental studies suggest that the concerted pathway is dominant while theoretical calculations have suggested that the homolytic pathway might require significantly less energy. We report here a third pathway:  (iii) successive HONO elimination to form 3 HONO (M = 47) plus stable 1,3,5-triazine (TAZ) (M = 81) with subsequent decomposition of HONO to HO (M = 17) and NO (M = 30) and at higher energies of TAZ into three HCN (M = 27). We examined all three pathways using first principles quantum mechanics (B3LYP, density functional theory), including the barriers for all low-lying products. We find:  A threshold at ∼40 kcal/mol for which HONO elimination leads to TAZ plus 3 HONO, while NN homolytic cleavage leads to RDR plus NO_2, and the concerted pathway is not allowed; above ∼52 kcal/mol the TAZ of the HONO elimination pathway can decompose into 3 HCN while the HONO can decompose into HO + NO; above ∼60 kcal/mol the concerted pathway opens to form CH_2NNO_2; at a threshold of ∼65 kcal/mol the RDR of the NN homolytic pathway can decompose into other products. These predictions are roughly consistent with previous experimental results and should be testable with new experiments. This should aid the development of a kinetic scheme to understand combustion and decomposition of solid-phase RDX and related energetic compounds (e.g., HMX).


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http://dx.doi.org/10.1021/jp9936953DOIArticle
http://pubs.acs.org/doi/abs/10.1021/jp9936953PublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/jp9936953PublisherSupporting Information
ORCID:
AuthorORCID
Dasgupta, Siddharth0000-0002-9161-7457
Goddard, William A., III0000-0003-0097-5716
Additional Information:© 2000 American Chemical Society. Received 18 October 1999. Published online 23 February 2000. Published in print 1 March 2000. This research was supported by a grant from the DOE-ASCI-ASAP. The MSC facilities activities are also supported by grants from NSF CHE (95-12279), Chevron Corp., ARO-MURI, Beckman Institute, Exxon, Owens-Corning, Avery-Dennison, Dow Chemical, 3M, NIH, Asahi Chemical, BP Amoco, and ARO ASSERT.
Funders:
Funding AgencyGrant Number
Department of Energy (DOE)UNSPECIFIED
NSFCHE 95-12279
Chevron CorporationUNSPECIFIED
Army Research Office (ARO)UNSPECIFIED
Caltech Beckman InstituteUNSPECIFIED
ExxonUNSPECIFIED
Owens-CorningUNSPECIFIED
Avery-DennisonUNSPECIFIED
Dow ChemicalUNSPECIFIED
3MUNSPECIFIED
NIHUNSPECIFIED
Asahi ChemicalUNSPECIFIED
BP AmocoUNSPECIFIED
Issue or Number:11
Record Number:CaltechAUTHORS:20170719-134437924
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170719-134437924
Official Citation:The Mechanism for Unimolecular Decomposition of RDX (1,3,5-Trinitro-1,3,5-triazine), an ab Initio Study Debashis Chakraborty, Richard P. Muller, Siddharth Dasgupta, and William A. Goddard, III The Journal of Physical Chemistry A 2000 104 (11), 2261-2272 DOI: 10.1021/jp9936953
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:79213
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:19 Jul 2017 21:22
Last Modified:03 Oct 2019 18:17

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