Comment by wnoise on 06/12/2023 at 19:33 UTC*

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For single-electron atoms, they really are spherical harmonics. Things get more complicated for multiple electron atoms, but the spherical harmonics remain a reasonably good approximate description. For molecular orbitals, spherical harmonics are often not good descriptions, but the "hybrid" orbitals from perturbation theory are.

The spherical harmonics have HUP uncertainty already built in by being delocalized and having a spread of momentum -- no need to sum over many (though in situations like multi-electron atoms and small molecules, it may still be a nice basis to expand over and do computations in).

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