DENSITY-FUNCTIONAL INVESTIGATION OF SOME DECOMPOSITION ROUTES OF METHYL NITRATE

Two density-functional methods, B3/LYP/6-31+G(d) and B3/PW91/6-31G(d, p) have been used to investigate some possible decomposition pathways for methyl nitrate. Two likely ones were found to be (a) loss of NO2, followed by eventual rearrangement to H2C-OH, and (b) formation of H2C =O and HONO. The initial energy requirement for each process-is about 40 kcal/mol, and the second is exothermic, Delta H = -16 kcal/mol of H 3C-ONO2. The B3/LYP procedure is found to underestimate the H3CO-NO2 a nd H3C-ONO2 dissociation energies by about 6 kcal/mol. (C) 1997 John W iley & Sons, Inc.