Write and retain the nuclear Coulomb potential. In spherical coordinates, the total potential energy is
when ; is a Legendre polynomial. Treat the added term using quadratic anisotropic perturbation of hydrogen and degenerate perturbation theory in the hydrogen energy eigenbasis. It preserves parity and , so it cannot mix with , or distinct magnetic sublevels.
For a hydrogen atom, the hydrogen radial second moment gives
The angular expectation values of are for an orbital, for , and for , obtained by integrating the squared spherical harmonics. Therefore the five lowest spatial quantum states, counting statistical weight, have first-order energy levels
Each spatial quantum state has two electron spin states when spin-orbit coupling and the magnetic field are omitted. Thus these are five spatial states but only three distinct first-order energies; five distinct energies would be an incorrect reading. The accidental equality can be lifted at higher order. Quantitatively the added shifts must also be small compared with neighboring principal-shell gaps; is an asymptotic condition, not a guarantee for arbitrary large .
Figure 1.
First-order spatial levels of locally perturbed hydrogen; the gap between principal shells is compressed
. Details.
For general , the expectation value is
It does not cancel every order. At , couples to orbitals. For example its angular matrix element with is , and the radial matrix element is nonzero. The second-order nondegenerate perturbation theory sum has negative denominators, so this is a concrete nonzero higher-order contribution.
There is also a global limitation: for either negative above, . A localized wavepacket translated far along has fixed kinetic energy but arbitrarily negative potential energy, proving there is no true lowest energy level. The results describe local perturbative resonance poles, or a potential completed to a confining form far from the atomic nucleus. No globally exact ground-state cancellation exists for the potential as printed.
An axially symmetric quadratic potential energy perturbation preserves parity and the component of orbital angular momentum. For , its first-order energy shifts are respectively , , , and . They follow by multiplying the hydrogen radial second moment by the angular average of , whose averages are . Negative makes the globally extended potential unbounded below; the shifts then describe local perturbative resonance poles or a potential stabilized at large distance.