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The fermion self-energy of an Electron in quantum electrodynamics. After renormalization, its contribution in a bound chemical atom is one source of the Lamb shift; other radiative corrections and nuclear structure also affect the observed energy levels.

For emission take integers $n_i>n_f\ge 1$. Applying conservation of energy to the model's internal energy difference, while neglecting the much smaller whole-atom photon recoil, givesThus Johannes Robert Rydberg's Rydberg formula is a difference of two energy levels expressed as a spectroscopic wavenumber. The same constants determine every line; there is no new parameter for each electronic transition. With the chosen inputs, $R_H=1.096775834\times 10^7{\mathrm{m}}^{-1}$. All wavelengths below are calculated in vacuum, not air, and are rounded model predictions rather than historical measurements.

The conventional names commemorate Theodore Lyman and Johann Jakob Balmer. Fixing $n_f=1$ produces the ultraviolet Lyman series, beginning with the Lyman-alpha line; fixing $n_f=2$ produces the Balmer series. As $n_i\to \infty$, the wavelength approaches $n_f^2/R_H$: $91.1763\mathrm{nm}$ at the Lyman limit and $364.705\mathrm{nm}$ for the Balmer series. Crowding follows directly from $E_{n+1}-E_n\sim 2B_H/n^3$. Discreteness therefore coexists with a series limit.

Correct line positions do not give wave intensities, lifetimes or electric-dipole selection rules for hydrogen. Those require a theory of the wavefunctions and their coupling to electromagnetic radiation. The circular model also omits spin, relativistic corrections and the Lamb shift. Its successful gross energy levels do not make its assumed orbits modern atomic orbitals.

Consider a fixed proton and one Electron, omitting spin, fine structure and the Lamb shift. Let $e>0$ be the elementary charge, $a_0$ the Bohr radius in this fixed-nucleus model, and $\mathbf{E}=\mathcal{E}\hat{\mathbf{z}}$. Because the Electron's electric dipole moment is $\mathbf{d}=-e\mathbf{r}$, its electric-dipole interaction isThe first excited hydrogen eigenspace has a common unperturbed energy eigenvalue $E_2$. Write $|s⟩=|2,0,0⟩$ and $|p_m⟩=|2,1,m⟩$ in the hydrogen energy eigenbasis. The electric-dipole selection rules for hydrogen leave only the $s,p_0$ coupling within this eigenspace. Each diagonal matrix element vanishes by parity, but that does not make the entire perturbation vanish. Degenerate perturbation theory requires its eigenvalues in the whole eigenspace. With the usual real wavefunction phases the off-diagonal position matrix element is $⟨s|z|p_0⟩=-3a_0$.^[ref]

The factor three can be checked directly. Set $\rho =r/a_0$ and use normalized radial wavefunctions and spherical harmonics:The angular integral is $\int Y_{00}^{\ast }\cos \theta Y_{10}d\Omega =1/\sqrt{3}$. Including $z=r\cos \theta$ and the radial volume factor $r^2$ then givesReversing the quantum phase of $|p_0⟩$ reverses this sign, with no change to the predicted energy eigenvalues.

Thus the nontrivial two-dimensional block and its determinant equation areConsequently, for the displayed sign convention,The two remaining energy eigenstates $|p_{+1}⟩,|p_{-1}⟩$ have zero first-order shifts. The slopes correspond to opposite electric dipole moments, $⟨d_z⟩=+3e{a}_0$ and $-3e{a}_0$. The electric field selects combinations of opposite parity that already have these dipole expectations at leading order. This is why applying first-order nondegenerate perturbation theory separately to $2s$ and $2p_0$, and obtaining two zero diagonal entries, misses the splitting.

The approximation requires $e{a}_0|\mathcal{E}|$ small compared with the separation to other principal quantum numbers. For real hydrogen atoms, it also requires the relevant electric-dipole interaction to dominate the small splittings omitted here, including the Lamb shift. At sufficiently small electric fields a pre-existing nonzero $2s$–$2p$ separation must be retained before taking the limit. A simple two-state illustration with unperturbed separation $\delta >0$ has shifts relative to its meanFor $3e{a}_0|\mathcal{E}|\ll \delta$, the lower branch moves by $-(3e{a}_0\mathcal{E}{)}^2/\delta +O({\mathcal{E}}^4)$ relative to its zero-field value. At $\delta =0$ the splitting is linear. This interpolation explains the importance of the hydrogen energy-level degeneracy; it is not a complete model of the fine structure multiplet.

The root mean square radius of the proton charge distribution. Finite nuclear size changes hydrogen atom energy levels and enters precision predictions for the Lamb shift.^[ref]