The structure of acetyl tetroxide intermediate: A theoretical study

A theoretical study on the geometries and relative conformational energies of CH3C(O)O2 and CH3C(O)O4H at the B3LYP and MP2 levels of theory has been carried out. It is revealed that the structures of CH3C(O)O4H can be categorized into Z-conformations and E-conformations with respect to the carbonyl group. The lowest-energy conformer of CH3C(O)O4H is stabilized by an internal hydrogen bond. Also these conformations have considerable stabilization energy with respect to CH3C(O)O2+HO2. Particularly, for most Z-conformations of CH3C(O)O4H, ΔG2980 is negative relative to that of CH3C(O)O2+HO2, indicating that these conformations are thermodynamically more stable than CH3C(O)O2+HO2.