Ab initio MODPOT/VRDDO/MERGE calculations on energetic compounds. I. Mechanism of initiation of cationic polymerization from electrostatic molecular potential contour maps

It had been observed experimentally in 1969 for cyclic ethers with conventional substituents that their propensity to polymerize was influenced by their basicities and ring strain. For energetic new polymers it was desired to predict the propensity of cyclic ethers substituted with energetic groups prior to synthesis of the monomers themselves. We carried out ab initio quantum chemical calculations on these energetic cyclic ethers and generated the electrostatic molecular potential contour maps. These maps vividly indicate the basicities of the cyclic ethers and permit the relative ranking of their tendencies to polymerize. The maps also allow optimal choice of good copolymer candidates.