Quantum chemical calculation of the primary thermolysis reactions of 1,1-diamino-2,2-dinitroethylene (FOX-7)

New Thermolysis Routes of Diaminodinitroethylene (DADNE)

“…This channel was distinguished in previous studies [12, 30] as the major channel of DADNE thermolysis since it has the lowest of the known channels activation enthalpy ( ΔH a ), which coincides with the experimental value [8, 9, 15, 16].…”

“…This is also the whole complex of reactions proceeding via the formation of the aci forms of DADNE with ΔH a ranging from 195 to 203 kJ mol −1 . These values correspond, as a whole, to the theoretical and experimental data [12, 23, 30]. Note that the reaction variant of hydrogen transfer to carbon with NO 2 detachment affords reactive species: radicals capable of reacting with DADNE and initiating thermolysis via the bimolecular mechanism.…”

“…A rather detailed theoretical study of the decomposition of DADNE ( 1 ) has been carried out elsewhere [12, 30]. In this work, we partially repeated these studies by our methods to compare the results of studying the reactions via these channels with new data.…”

“…The detachment of HNO 2 is accompanied by the rearrangement of the remained nitro group to the oxo (=O) and nitroso (−N=O) groups via TS12 (the numbering of the states from [30]) to form P12…HNO 2 complex, which further decomposes to the following products (Scheme 2).…”

Quantum chemical investigation of the 1‐methyl‐ and 1‐neopentyl‐2‐methoxydiazene‐1‐oxides thermal decomposition mechanisms

“…Both of these calculation levels are versions of the CCSD method and produce similar results. The calculation level CCSD/aug‐cc‐pVDZ//PBE0/cc‐pVDZ was chosen because for diaminodinitroethylene (DADNE) and its various derivatives it reproduced well the results obtained at higher calculation levels, [ 30–34 ] and these data correspond to the experiment. According to Krisyuk and Krisyuk et al, [ 31,33 ] it is sufficient to use the CCSD method for this kind of calculations.…”