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I am writing a small program to animate electronic transitions.

To do this, I am animating a Rabi cycle for a single electron as it moves from an occupied into a virtual orbital.

The on-resonance excitation process during the interaction of a molecule with a coherent laser is modelled by the Rabi formula: $$\Psi = \cos(\Omega_R)\Psi_g + \sin(\Omega_R) \Psi_e e^{-i\omega t},$$

where $\Omega_R$ is the Rabi frequency and $\omega = (E_e - E_g)/\hbar$.

As a minimal example, I will consider the $\ce{H2}$ molecule. The first electronic excitation is $\sigma \rightarrow \sigma^*$.

Formally, the wave function of the ground state is: $\Psi_g = \det|\sigma_{\alpha}\sigma_{\beta}|$, and the excited state is: $\Psi_e = \det|\sigma^*_{\alpha}\sigma_{\beta}|$.

Intuitively, I think that the description of the excitation process can be understood by considering only the wave function of an isolated electron jumping from a $\sigma_\alpha$ into a $\sigma_{\alpha}^{*}$ orbital, rather than wave function as a whole. In this case, I express the transition state as follows:

$$\Psi = \cos(\Omega_R) \sigma_{\alpha} + \sin(\Omega_R) \sigma^*_{\alpha} e^{-i\omega t}$$

from which an animation of the changing electron density can be constructed by computing isosurfaces of $|\Psi(t)^{2}|$, and assigning the color depending on the phase of the underlying wavefunction at that point:

H2 excitation

In a more complicated molecule, the same simplification might correspond to expressing the excitation process as follows:

$$\Psi = \cos(\Omega_R) \psi_{\text{HOMO}(\alpha)} + \sin(\Omega_R) \psi_{\text{LUMO}(\alpha)} e^{-i\omega t}$$

Which, for an s-tetrazine derivative leads to the following animation for the first excited state (side and top view):

3,6-dimethyoxy-s-Tetrazine

My issue is that I am not 100% certain about whether there is a formal procedure that allows me make the claim that these animations provide me with a physically valuable description of what happens during an excitation. It is clear to me that these animations do allow us to understand the symmetry rules and the direction of the transition dipole moment. I am looking for some help in finding the formal way of justifying this approach. Could the "1 particle reduced density matrix" formalism help me here?

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    $\begingroup$ Welcome! May I suggest checking out FAQ: How can I format math/chemistry expressions on Chemistry Stack Exchange?. You obviously know the syntax already (most of it is identical to LaTeX); but there are some things which you will find useful, e.g. using \cos{...} instead of just cos ... to correctly typeset cosine and other operators. $\endgroup$
    – orthocresol
    Nov 2 at 13:23
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    $\begingroup$ Aren't you running (besides details which I might not understand) in the problem to give physical sense to the orbitals, the most usual way to do it being its interpretation as a probability distribution function? $\endgroup$
    – Alchimista
    Nov 2 at 13:56
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    $\begingroup$ @Alchimista, I should have been a bit more specific about the final step, I will make an edit to clarify. What I animate is the wave function squared, where the wave function is the time-dependent wave function during the Rabi cycle. So, the physical interpretation would indeed be the changing probability distribution of a single electron during the excitation process. I think that this makes intuitive sense. If only one electron changes orbital, then we only have to consider the changing probabilities for that single electron. But I do not know how to justify this assertion formally! $\endgroup$
    – MaxParadiz
    Nov 2 at 14:12
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    $\begingroup$ @MaxParadiz I see now. You are looking for something like a energy bases criterion of separation. I am sure specialist will help you. Otherwise try finding done examples, if the final rendering is your main goal. $\endgroup$
    – Alchimista
    Nov 2 at 14:56
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    $\begingroup$ I'm not sure you can formally justify this approach. Electrons are indistinguishable and therefore it is formally incorrect to localize one electron to one orbital and the other to the other orbital. The full wave function of the system includes contributions from each electron in both orbitals. But there's still no reason why you can't make an animation of only one orbital of the excited state. $\endgroup$
    – Andrew
    Nov 2 at 19:30
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The answer here depends on what you mean by "formal procedure" and "physically valuable".

The potential flaw in your approach is the assumption that

$$\Psi=\cos(\Omega_R)\sigma_\alpha + \sin(\Omega_R)\sigma^*_\alpha e^{−i\omega t}$$

is a valid description. Formally, the wave function of a two-electron system cannot be split into two independent one-electron wave functions. This is perhaps more clear if you write out the full determinants in the wave functions, which are $$\Psi_g=\begin{vmatrix}\sigma_\alpha(1)&\sigma_\beta(1)\\\sigma_\alpha(2)&\sigma_\beta(2)\end{vmatrix}$$ and (for a singlet excited state) $$\Psi_e=\begin{vmatrix}\sigma_\alpha(1)&\sigma^*_\beta(1)\\\sigma_\alpha(2)&\sigma^*_\beta(2)\end{vmatrix}$$

where (1) and (2) are the two electrons and $\alpha$ and $\beta$ are spin states.

That is, each wave function necessarily consists of contributions from each possible electron-orbital pairing rather than just assigning one electron to each orbital. (For a triplet excited state, there are actually two additional wave functions to account for the spin possibilities, but that's not necessary to consider for this discussion.)

That said, almost all computational approaches to dealing with such systems apply this invalid approach in order to make the mathematics tractable. The Hartree-Fock method is a very common starting point. By adding various terms to correct for the indistinguishability and interactions of the electrons, the results of these methods can approach the results we would expect to get from a formally correct description of the system (ie solving the Schrodinger equation for a single multi-electron wave function).

Furthermore, treating the total electron density of a molecule (ie the square of the multi-electron wave-function) as the sum of densities of multiple discrete orbitals is a standard pedagogical approach, and predicting the properties and reactions of molecules based on a subset of these discrete orbitals (valence or frontier orbitals usually) works quite well at a qualitative and semi-quantitative level. Whether this pedagaogical value counts as "physically valuable" depends on what you mean by that.

I'll conclude by invoking George Box's maxim that "All models are wrong. Some are useful." While your animations are not defensible on theoretical physics grounds, that does not mean that they are not reasonable and useful representations for pedagogical purposes.

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