Thermal dissociation of 1,2‐dioxethane. I. Charge density distribution along the reaction path and in different HF solutions

A charge density distribution study, based on ab initio SCF–6‐31G wave functions, on the optimized geometry of 1,2‐dioxethane indicates its high instability which results from (i) the high ring strain, (ii) the large amount of charge contained on the nonbonded sides of the oxygen nuclei, and (iii) the weak binding character of the charge density in the OO bond region. The redistribution of the charge density when 1,2‐dioxethane undergoes change in its nuclear configuration has been discussed. This redistribution of charge along the reaction path (the dissociation of 1,2‐dioxethane to formaldehyde products) shows clearly the preceding nature of the electron cloud. The characteristic features of the charge density distribution of the two Hartree–Fock solutions to which the SCF procedure converges have been analyzed and discussed.