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Titolo:
Mechanism for unimolecular decomposition of HMX (1,3,5,7-tetranitro-1,3,5,7-tetrazocine) an ab initio study
Autore:
Chakraborty, D; Muller, RP; Dasgupta, S; Goddard, WA;
Indirizzi:
CALTECH, Beckman Inst 139 74, Mat & Proc Simulat Ctr MSC, Div Chem & Chem Engn, Pasadena, CA 91125 USA CALTECH Pasadena CA USA 91125 iv Chem & Chem Engn, Pasadena, CA 91125 USA
Titolo Testata:
JOURNAL OF PHYSICAL CHEMISTRY A
fascicolo: 8, volume: 105, anno: 2001,
pagine: 1302 - 1314
SICI:
1089-5639(20010301)105:8<1302:MFUDOH>2.0.ZU;2-4
Fonte:
ISI
Lingua:
ENG
Soggetto:
CONDENSED-PHASE DECOMPOSITION; GASEOUS PYROLYSIS PRODUCTS; THERMAL-DECOMPOSITION; ENERGETIC MATERIALS; DYNAMICS SIMULATIONS; TEMPORAL BEHAVIORS; MASS-SPECTROMETRY; RDX; OCTAHYDRO-1,3,5,7-TETRANITRO-1,3,5,7-TETRAZOCINE; COMBUSTION;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Physical, Chemical & Earth Sciences
Citazioni:
46
Recensione:
Indirizzi per estratti:
Indirizzo: Goddard, WA CALTECH, Beckman Inst 139 74, Mat & Proc Simulat Ctr MSC, Div Chem & Chem Engn, Pasadena, CA 91125 USA CALTECH Pasadena CA USA 91125 em Engn, Pasadena, CA 91125 USA
Citazione:
D. Chakraborty et al., "Mechanism for unimolecular decomposition of HMX (1,3,5,7-tetranitro-1,3,5,7-tetrazocine) an ab initio study", J PHYS CH A, 105(8), 2001, pp. 1302-1314

Abstract

To improve the mechanistic understanding of the possible decomposition in the gas phase of the energetic material HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine), we used ab initio calculations to determine the various unimolecular decomposition channels. We find three distinct mechanisms: (i) homolytic cleavage of N-N bond to form NO2 (M = 46) and HMR (M = 250) which subsequently decomposes to form various products (ii) successive HONO eliminations to give four HONO (M = 47) plus a stable intermediate (M 108); (iii) O-migration from one of the NO2 groups of HMX to neighboring C atom followed by the decomposition of intermediate (M = 296) to INT222 (a ring-opened RDX structure) and MN-oring (M = 74), which can undergo dissociation to smaller mass fragments. The decomposition scheme for HMX is similar to that for RDX presented earlier (J. Phys. Chem. A 2000, 104, 2261), except that concerted decomposition of HMX to four MN (M = 74) molecules is not a favorable decomposition pathway, whereas this pathway was found in RDX decomposition (both experimentally and theoretically). The formation of RDR-o in the N-N homolysis pathway 1 or the formation of INT222 in pathways 1 and 3 presents an unified mechanistic scheme for the decomposition of both of these nitramines. The HMX decomposition mechanism correlates with available condensed phase experimental results, but detailed comparison of the predictedgas phase energetics is not possible.

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Documento generato il 12/07/20 alle ore 06:40:36