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VSEPR theory correctly predicts the shapes of many symmetry-broken molecules such as $\ce{H2O}$ and $\ce{NH3}$. Take $\ce{NH3}$ for example. In VSEPR theory, the nitrogen atom is (approximately) at the center of a tetrahedron, the three $\ce{N-H}$ bonds point to three of the four vertices of the tetrahedron, and the lone pair of nitrogen points to the $4$th vertex. But quantum mechanically speaking, the electrons should all be delocalized in the entire $\ce{NH3}$ molecule. How do I unify the two pictures to understand the concept of chemical bonds and VSEPR theory in quantum mechanics? Does VSEPR correspond to some kind of trial wave function (e.g. antisymmetrized geminal power (AGP))?

Note: when I say how to understand chemical bonds in quantum mechanics, I mean in the chemical bond description of molecules, electron pairs are localized at the bonds while quantum mechanics again says everything can be delocalized. So it's the same discussion as VSEPR v.s. QM. If there are only two atoms and one bond, the quantum mechanical meaning of the chemical bond is clear.

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    $\begingroup$ If you already know a bit about QM then ignoring VSEPR altogether seems like a good idea to me. $\endgroup$ – Mithoron Jan 21 '18 at 20:49
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    $\begingroup$ You can obtain localised MOs by a unitary transformation of the canonical ("delocalised") MOs, en.wikipedia.org/wiki/Localized_molecular_orbitals The LMOs can in turn be related to the simple VSEPR ideas of bond pairs / lone pairs. $\endgroup$ – orthocresol Jan 21 '18 at 20:53
  • $\begingroup$ VSEPR isn't exactly good even for water chemistry.stackexchange.com/a/41206/9961 $\endgroup$ – Mithoron Jan 21 '18 at 21:10
  • $\begingroup$ @orthocresol, I think before that we need some kind of independent pair approximation to allow us think about one pair of electrons at a time. AGP seems to be a good choice, but I'm not yet sufficiently familiar with it. $\endgroup$ – Zhuoran He Jan 21 '18 at 21:10
  • $\begingroup$ If your problem with VSEPR theory is that it assumes some independence between electron pairs, then yeah, of course; it cannot replicate the full correlation in the true wavefunction. Then again, nothing does it perfectly, so. $\endgroup$ – orthocresol Jan 21 '18 at 21:20
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VSEPR is a simple and generalised approach based (mainly) on empirical observation. It is a great theory in predicting, in a first order approximation, the geometrical shape of molecules. That is a lot harder with other methods. It is of course based on a physical foundation, not only empiricism. You might want to explore electron-domains and the Pauli principle in this context.

There have been a lot of post-rationalisations that cause more harm than good, because they clearly go beyond the limitations of the theory. One of the most miss-taught ones is the involvement of d-orbitals in hybridisation schemes, but that comes from the lack of understanding of some instructors, and its confusion with valence bond theory.
One of the most prominent examples where it (basically) fails is outlined in my answer here: Are the lone pairs in water equivalent? At this point it should be noted, that the general topology of the electron density is quite well reproduced.

With that in mind, a reconciliation of this empirical approach with quantum theory to understand bonding is dangerous, if not futile. It should be used for providing a reasonable guess for a molecular structure and its principle explanation. Anything beyond that might lead to wrong conclusions. It cannot, in any way, be used to generate a guess for a wave function, because it is not based on it.

You will have to use another method for that. Often confused with VSEPR is the valence bond theory (VBT). It cannot be stressed enough, that the two are completely independent (even at its crudest level). There has been a lot of development in that field, and what is often taught as VBT can only be classified as a very crude approximation. It is in principle an exact theory, but carried out at the theoretical limit is not as easily understood as that what is taught commonly. (Just have a look at resonance, and its misconceptions as are outlined here: What is resonance, and are resonance structures real?)
Another way to describe bonding is molecular orbital theory (MOT), which already comes with the necessary properties of electron delocalisation. Unfortunately, this theory is more difficult to get started in, and does not provide an easy picture to follow. The good thing about this is, that it doesn't get much more complicated at its theoretical limit.
The two approaches are at their respective theoretical limit (VBT decribes electron correlation via resonance structures, MOT need multiple determinants for this) equivalent.

Understanding bonding is not easy and it is by far not without controversy. Even at approximate VBT or MOT there can be many misconceptions, and incorrect deductions, conclusions, rationalisations. For everything in the "grey" areas, there are opinions, interpretations, and opinions about interpretations.
In any and every case one should always be aware of the limitations of the model used. One should also be critical about the found results. One should always expect everything to be a lot more complicated than expected (point in case: CO2).
If you keep all of that in mind: VSEPR is an awesome model system.

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