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Heats of formation and thermal stability of substituted 1,1′‐Azobis(tetrazole) compounds with an extended nitrogen chain
Author(s) -
Pimienta Ian,
Patkowski Konrad
Publication year - 2019
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.25794
Subject(s) - tetrazole , chemistry , standard enthalpy of formation , decomposition , density functional theory , nitrogen , thermal decomposition , computational chemistry , exothermic reaction , ab initio , radical , thermal stability , ab initio quantum chemistry methods , organic chemistry , molecule
The molecular structures of 1,1′‐Azobis(tetrazole) (N 10 ) and monosubstituted compounds involving F, CH 3 , CN, NH 2 , OH, OCH 3 , N 3 , NF 2 , NO 2 , and CH 2 NO 2 groups are investigated using density functional theory. The heats of formation of these compounds are investigated using ab initio composite methods. Intrinsic reaction coordinate calculations are performed to determine the energies along the decomposition pathways. The optimized geometries of the N 10 compounds indicate planar configurations consisting of aromatic nitrogen–nitrogen and carbon–nitrogen bonds. The stability and energy content of the substituted compounds are highly correlated with the nature of the substituents. Electron‐donating groups reduce the heats of formation but increase the exothermicity of the decomposition. The decomposition of the N 10 compounds is classified into two general pathways: (1) a scheme involving straight‐up decomposition and (2) a scheme involving functional rearrangement. Compounds undergoing decomposition pathway (1) are more exothermic with lower rate‐determining activation barriers than those undergoing the latter pathway (2).