Abstract:

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