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In Kohn-Sham DFT, the exact density of the ground-state wavefunction is given by summing the squares of the filled K-S orbitals.

Suppose now that one only needs the exact density (and nothing else w.l.o.g; see this open-access article e.g. for the derivation of the exact optical gap from the excited density of, say, the lowest doubly (for each spin) excited state, of the molecule in question. Does summing the squares of the K-S orbitals, except for the HOMO (which would now be swapped with the LUMO) give the desired density of said state?

EDIT: I meant the lowest doubly excited SINGLET state with the ground state also being singlet.

EDIT 2: wzkchem5's counterexample seems to be mostly correct, but their formation of their answer likely implies that the ground state of the total wavefunction itself is degenerate. So I'm explicitly adding in the condition that the ground state is non-degenerate, as is in the theoretical foundation of K-S DFT.

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In general, no. Consider an infinitely stretched dihydrogen molecule, in its ground (singlet) state. Obviously the HOMO is the in-phase linear combination of the 1s orbitals of the neutral hydrogen atoms, and the LUMO is their out-of-phase linear combination. (The shape of the HOMO follows from the fact that the density of the system must be equal to a sum of the densities of two neutral hydrogen atoms, and the shape of the LUMO follows from the fact that the Kohn-Sham potential is local, thus the LUMO of this molecule must be locally identical to the HOMO up to a phase.) A corollary is that, the square of the LUMO is the same as the square of the HOMO. (EDIT: more rigorously speaking, their difference is non-zero for finitely stretched hydrogen molecules but vanishes in the infinitely stretched limit.)

Now excite the molecule to the lowest doubly excited singlet state. It follows that in this state, at least one of the electrons must populate an atomic orbital other than the 1s orbital (EDIT: a molecular orbital involving significant contribution from a non-1s atomic orbital), since there are only three singlet states constructible from the two 1s orbitals and two electrons (the ground state and two charge transfer states: $$\frac{1}{\sqrt{2}}(\psi_{\rm H1}(r_1)\psi_{\rm H2}(r_2) + \psi_{\rm H1}(r_2)\psi_{\rm H2}(r_1)), \psi_{\rm H1}(r_1)\psi_{\rm H2}(r_1), \psi_{\rm H1}(r_2)\psi_{\rm H2}(r_2)$$ The fourth linear combination constructible from the four Slater determinants, $\frac{1}{\sqrt{2}}(\psi_{\rm H1}(r_1)\psi_{\rm H2}(r_2) - \psi_{\rm H1}(r_2)\psi_{\rm H2}(r_1))$, is a triplet state), none of which is a doubly excited state. Therefore the density of this excited state cannot be given as twice the square of the LUMO. QED.

The conclusion may seem a bit non-intuitive; many will immediately say "isn't the $({\rm HOMO})_2 \to ({\rm LUMO})_2$ excitation a double excitation?" This reveals a fundamental difference between the Kohn-Sham and HF descriptions of this system. In HF, the closed-shell ground state wavefunction of this system can be expanded in atomic orbitals (neglecting the spin part):

$$ \psi_{\rm HF} = \frac{1}{2}(\psi_{\rm H1}(r_1)\psi_{\rm H2}(r_2) + \psi_{\rm H1}(r_2)\psi_{\rm H2}(r_1) + \psi_{\rm H1}(r_1)\psi_{\rm H2}(r_1) + \psi_{\rm H1}(r_2)\psi_{\rm H2}(r_2)) \tag{1} $$

The latter two terms are spurious intermixtures of charge transfer states, which are famously responsible for the size-inconsistency of RHF. In this case we can formally write the $({\rm LUMO})_2$ determinant

$$ \tilde{\psi}_{\rm HF} = \frac{1}{2}(\psi_{\rm H1}(r_1)\psi_{\rm H2}(r_2) + \psi_{\rm H1}(r_2)\psi_{\rm H2}(r_1) - \psi_{\rm H1}(r_1)\psi_{\rm H2}(r_1) - \psi_{\rm H1}(r_2)\psi_{\rm H2}(r_2)) \tag{2} $$

But this is just as unphysical as the RHF description of the ground state, again due to the charge transfer state contributions.

The Kohn-Sham wavefunction can of course be expanded as Eq. (1) as well, but a more important thing is that, the ground state Kohn-Sham density must equal the exact density, given by the exact wavefunction:

$$ \psi_{\rm exact} = \frac{1}{\sqrt{2}}(\psi_{\rm H1}(r_1)\psi_{\rm H2}(r_2) + \psi_{\rm H1}(r_2)\psi_{\rm H2}(r_1)) \tag{3} $$

while the exact wavefunction of the first doubly excited state inevitably involves the 2s and/or 2p orbitals (EDIT: inevitably involves molecular orbitals that have large contributions from the 2s and/or 2p orbitals), and cannot have any simple relation with the exact ground state wavefunction, as we do in the RHF case. Therefore, while $({\rm LUMO})_2$ is a valid KS determinant, it does not have any simple relation with the density of the first doubly excited state.

Finally, there is one more thing to consider: doubly excited states are not well-defined concepts, especially in complex molecules, because the doubly excited determinants may mix extensively with singly excited determinants, making it impossible to unambiguously assign some states as singly or doubly excited. Thus, in some cases your question may not even be well-defined.

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  • $\begingroup$ "Now excite the molecule to the lowest doubly excited singlet state. It follows that in this state, at least one of the electrons must populate an atomic orbital other than the 1s orbital, since there are only three singlet states constructible from the two 1s orbitals and two electrons": the two electrons would populate the 1s orbitals- the antibonding combination to be specific. $\endgroup$ Nov 3, 2022 at 1:07
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    $\begingroup$ I have edited the post to show why there are only three singlet states. Note that you may either work under the many-body wavefunction picture or the Kohn-Sham picture, but not both. If you consider the many-body wavefunctions, then (HOMO)2 and (LUMO)2 are not eigenstates, and it's meaningless to say that the two electrons would populate the antibonding combination of the 1s orbitals. If you consider the Kohn-Sham orbitals, then the ground state is (HOMO)2, but that does not mean (LUMO)2 is an excited state, since for excited states the Hohenberg-Kohn theorem does not hold. $\endgroup$
    – wzkchem5
    Nov 3, 2022 at 6:03
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    $\begingroup$ The square of the LUMO is indeed the same as the square of the HOMO when the hydrogen atoms are infinitely separated from each other. Using your notation, the ab cross term vanishes identically throughout the real space in this limit, because in this limit the 1s orbitals of the two hydrogen atoms do not overlap. $\endgroup$
    – wzkchem5
    Nov 3, 2022 at 6:06
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    $\begingroup$ Of course the HOMO and LUMO are not atomic orbitals, but rather linear combinations of them. But one can always express the wavefunctions under the AO basis instead of the MO basis, and then we can meaningfully talk about the occupation number expectation values of atomic orbitals, although they may not be integers. Nevertheless, I have edited the post so that it makes sense even under the pedantic view "AOs cannot be occupied, only MOs can". $\endgroup$
    – wzkchem5
    Nov 3, 2022 at 6:11
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    $\begingroup$ @KanghunKim in the future, please refrain from making new chat rooms. The site likes to prompt to do so, but we find that it makes it hard to track discussions and leads to a lot of old abandoned rooms. See this meta post for a discussion on how to get comments moved to an existing chat room. $\endgroup$
    – Tyberius
    Nov 3, 2022 at 15:42

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