Invisible spin allowed transitions in Tanabe-Sugano diagrams

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In class we are looking at Tanabe-Sugano diagrams, more concretely at transitions for a d2 complex.

I understand that the only spin allowed transitions are those that have a triplet state, therefore that there
are 3 spin allowed transitions

3T
1g (P) <- 3T1g (F)

3A
2g (F) <- 3T1g (F)

3T
2g (F) <- 3T1g (F)

These can be seen in the diagram. In addition, were are given the orbital occupancies for each energetic
state some of which I have attached for clarity.
From the occupancy image, it can be seen that the 3A2g state corresponds to both d electrons being in the
high energy eg orbitals. Hence my question is what process can lead to both electrons being in such an
excited state? Is it possible for a photon to excite both electrons at the time? Which I had never heard of
before, or is it that in order to achieve the 3A2g excited state, 2 photons need to be absorbed in rapid
succession, going through an intermediate excited state?

If two photons need to be absorbed does that effectively make the 3A2g state "impossible" to reach and
thus the absorption band isn't seen?

Thanks for your help.

inorganic-chemistry transition-metals uv-vis-spectroscopy

Share Cite Improve this question Follow asked Apr 10, 2021 at 16:16
Palamalama
51 2

It is better to imagine as the energy is absorbed by the whole system not by individual electrons. Two-electron
excitations exist (simultaneous, not just one by one). – Greg Apr 11, 2021 at 5:33

1 Two photon absorption is well known using short pulsed lasers as high flux is needed, but only on electron is
promoted. (Different selection rules also apply) To get two electrons excited will need two absorptions one after the
other, probably at different energies, so v. v. hard to achieve in practice as excited species always decay rapidly back
to the ground state. In a thought experiment, of course, you may be able to excite an excited state again to reach the
state you want. – porphyrin Apr 11, 2021 at 9:00