A New View of Relationships of the N-N Bond Dissociation Energies of Cyclic Nitramines. Part I. Relationships with Heats of Fusion


Atalar T., Zeman S.

JOURNAL OF ENERGETIC MATERIALS, vol.27, no.3, pp.186-199, 2009 (Journal Indexed in SCI) identifier identifier

  • Publication Type: Article / Article
  • Volume: 27 Issue: 3
  • Publication Date: 2009
  • Doi Number: 10.1080/07370650802640341
  • Title of Journal : JOURNAL OF ENERGETIC MATERIALS
  • Page Numbers: pp.186-199
  • Keywords: bond dissociation energy, cyclic nitramines, heat of fusion, N-N bond, ENERGETIC MATERIALS, SENSITIVITIES

Abstract

The values of bond dissociation energies, BDE, of the weakest N-N bonds and total energies, Etotal, of molecules have been calculated for 14 cyclic nitramines by means of the UB3LYP/6-31G* and UB3LYP/6-31+G* // PM3 methods. The relationships found between the BDE values and values of heat of fusion, Hm,tr, of these nitramines are not unambiguous. More unambiguous and logical relationships result from comparison of the BDE/Etotal ratio and the Hm,tr values. The dependences found appear suitable for prediction of the Hm,tr values for cis-1,3,4,6-tetranitrooctahydroimidazo[4,5-d]imidazole (31.89 kJ mol-1), 4,8,10,12-tetranitro-2,6-dioxa-4,8,10,12-tetraazaisowurtzitane (41.73 kJ mol-1), and 4,6,10,12-tetranitro-2,8-dioxa-4,6,10,12-tetraazaisowurtzitane (41.67 kJ mol-1); the predicted values of Hm,tr are within the expected limits and can represent a stabilizing effect of crystal lattice in decomposition reactions of the studied compounds in their molecular crystals.