Acta Phys. -Chim. Sin. ›› 1998, Vol. 14 ›› Issue (01): 33-38.doi: 10.3866/PKU.WHXB19980107

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Theoreticl Studies on the Pyrolysis of Polynitric Esters

Gong Xue-Dong, Xiao He-Ming   

  1. Department of Chemistry,Nanjing University of Science and Technology,Nanjing 210094
  • Received:1997-04-28 Revised:1997-06-16 Published:1998-01-15
  • Contact: Xiao He-Ming


The pyrolysis reactions of four polynitric esters at twelve conformations have been calculated using SCF-MO-AM1 method at RHF and UHF levels respectively. It has been found that homolysis of O-NO2 bond into two radicals RCH2O•and •NO2 has lower activation energy and is the main path way of pyrolysis. α-H transition elimination reaction of breaking O-NO2with the products RCHO and HONO has quite high activation energy. A good linear relationship exists between the activation energy of homolysis of O-NO2 and the Wiberg bond order of this bond.

Key words: Nitric esters, Conformation, Pyrolysis, Activation energy, AMlmethod, RHF calculation, UHF calculation