I'd like to investigate into the ring opening, the migratory reverse reaction of the electrocyclic ring-closure of Dimethyldioxirane:
As a first question I'd like to ask if I have drawn the through bond interaction correctly?
Following scheme is wrong, because the p orbitals are perpendicular to the O-C-O as @ron clearly pointed out in his answer in Are the p orbitals of the biradical dioxo compound in the HOMO perpendicular to the plane?
Next I tried to draw the orbital correlation diagram. I guess for this correlation diagram I don't have to draw the through bond interaction, yes?
- In the dioxo biradical product I've drawn a smaller energy gap between $\pi$ and $\pi^*$ orbitals as for $\sigma$ and $\sigma^*$. I guess this should be correct.
- Because there is an additional through bond interaction for the product I've drawn a small exothermicity. I see no activation energy for the disrotatory ring opening. So the disrotatory ring opening must happens very fast (without a lot of thermal energy, may be even at room temperature).
Finally, I tried to draw the state correlation diagram:
- For the photochemical reaction there is a transition from $S_0$ to $S_2$. Because of the avoided crossings the conrotatory correlation is steeper falling down, therefore I expect most of the electrons direcetly going in the pericyclic minimum and do there Interal Conversion to the $S_1$ surface and afterwards the excited product gives off a photon going back to the $S_0$ state. I expect products in excited states are not very long living and therefore undergoes emission of a photon as Internal Conversion under fluorescence here.
- Another way out from the pericyclic minimum can be the directly falling to the transition state of the $S_0$ state and giving the product to a good quantum yield.
- As third option some part of the $S_2$ states can go through the disrotatory pathway and directly emitting light from $S_2$ to $S_0$. As written in the first point I think this way is less probable because of the less steeper falling down the energy surface.
Is this all correct?