caa a22 4500 465818536 CHVBK 20180323112129.0 cr unu---uuuuu 170327e19901101xx s 000 0 eng 10.1007/BF01374527 doi (NATIONALLICENCE)springer-10.1007/BF01374527 Computational analysis of some possible initial steps in the unimolecular thermal decompositions of 1,3-diazacyclobutane and its 1,3-dinitramine derivative [Elektronische Daten] [Michael Grodzicki, Jorge Seminario, Peter Politzer] Summary: We have investigated some possible initial steps in the unimolecular thermal decompositions of 1,3-diazacyclobutane and its 1,3-dinitramine derivative, the latter being selected as the simplest example of a symmetric cyclic nitramine. Vibrational analyses were used to identify normal modes that, in the extreme limits, would correspond to bond rupture and molecular decomposition. The energy requirements for ring fragmentation and N-N bond-breaking were computed at the MP4/6-31G level, using SCF 3-21G optimized structures. It was concluded that ring-fragmentation is a probable initiating step in the decomposition of the unsubstituted molecule, and that it is roughly competitive with N-N bond scission for the dinitramine. The nitronitrite rearrangement is predicted, on the basis of SCF calculations, to be less likely than either of the other two processes. It is proposed that N-N bond-breaking may be of primary importance for nitramine stability, but that energetic performance may be determined more by decomposition pathways having energy barriers. Springer-Verlag, 1990 Nitramines nationallicence Vibrational analysis nationallicence Thermal decomposition nationallicence Activation energies nationallicence Dissociation energies nationallicence Grodzicki Michael Department of Chemistry, University of New Orleans, 70148, New Orleans, LA, USA aut Seminario Jorge Department of Chemistry, University of New Orleans, 70148, New Orleans, LA, USA aut Politzer Peter Department of Chemistry, University of New Orleans, 70148, New Orleans, LA, USA aut Theoretica chimica acta Springer-Verlag 77/6(1990-11-01), 359-367 0040-5744 77:6<359 1990 77 214 https://doi.org/10.1007/BF01374527 text/html Onlinezugriff via DOI 1 research-article jats NATIONALLICENCE 856 40 https://doi.org/10.1007/BF01374527 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Grodzicki Michael Department of Chemistry, University of New Orleans, 70148, New Orleans, LA, USA aut NATIONALLICENCE 700 1- Seminario Jorge Department of Chemistry, University of New Orleans, 70148, New Orleans, LA, USA aut NATIONALLICENCE 700 1- Politzer Peter Department of Chemistry, University of New Orleans, 70148, New Orleans, LA, USA aut NATIONALLICENCE 773 0- Theoretica chimica acta Springer-Verlag 77/6(1990-11-01), 359-367 0040-5744 77:6<359 1990 77 214 Metadata rights reserved Springer special CC-BY-NC licence nationallicence BK010053 XK010053 XK010000 NATIONALLICENCE NATIONALLICENCE NL-springer