title: Decomposition mechanisms and kinetics of novel energetic molecules BNFF-1 and ANFF-1: quantum-chemical modeling.
abstract: Decomposition mechanisms, activation barriers, Arrhenius parameters, and reaction kinetics of the novel explosive compounds, 3,4-bis(4-nitro-1,2,5-oxadiazol-3-yl)-1,2,5-oxadiazole (BNFF-1), and 3-(4-amino-1,2,5-oxadiazol-3-yl)-4-(4-nitro-1,2,5-oxadiazol-3-yl)-1,2,5-oxadiazole (ANFF-1) were explored by means of density functional theory with a range of functionals combined with variational transition state theory. BNFF-1 and ANFF-1 were recently suggested to be good candidates for insensitive high energy density materials. Our modeling reveals that the decomposition initiation in both BNFF-1 and ANFF-1 molecules is triggered by ring cleavage reactions while the further process is defined by a competition between two major pathways, the fast C-NO₂ homolysis and slow nitro-nitrite isomerization releasing NO. We discuss insights on design of new energetic materials with targeted properties gained from our modeling.
authors.affiliation: Materials Science and Engineering Department, University of Maryland, College Park, MD 20742, USA.
authors.forename: Roman V
authors.initials: RV
authors.lastname: Tsyshevsky
authors.forename: Maija M
authors.initials: MM
authors.lastname: Kuklja
mesh_terms: D007700:Kinetics; D008956:Models, Chemical; D015394:Molecular Structure; D010069:Oxadiazoles / Q000737:chemistry*; D011789:Quantum Theory
chemical_list: C587170:3,4-bis(4-nitro-1,2,5-oxadiazol-3-yl)-1,2,5-oxadiazole; C587171:3-(4-amino-1,2,5-oxadiazol-3-yl)-4-(4-nitro-1,2,5-oxadiazol-3-yl)-1,2,5-oxadiazole; D010069:Oxadiazoles