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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.

Define $\hslash {\omega }_0=E_2-E_1$ and use radiation energy density $u(\omega )$ per unit angular frequency, excluding the zero-point contribution. The Angular-frequency Einstein coefficients give rates per atom: $B_{12}u({\omega }_0)$ for absorption, $B_{21}u({\omega }_0)$ for stimulated emission, and $A_{21}$ for spontaneous emission. Stimulated emission adds a photon to the stimulating mode; spontaneous emission persists with no incident photons.

In thermal equilibrium the Boltzmann distribution gives $N_2/N_1=e^{-\hslash {\omega }_0/(k_{\mathrm{B}}T)}$. Balancing up and down rates yieldsMatching the Planck law for every temperature fixesNo degeneracy factor is needed for these nondegenerate levels.^[ref]

For plates of large area $A$ and spacing $d$, the surviving low-frequency transverse electromagnetic mode has one polarization, $\mathbf{E}\parallel \hat{\mathbf{z}}$, and in-plane wavevector. Periodic in-plane counting givesMultiplying this single-polarization two-dimensional photon density of states by $\hslash \omega$ and the Bose-Einstein distribution produces the thermal radiation between parallel conducting plates:The same rate balance therefore givesThese $B$ coefficients refer to the radiation polarization in their respective environments: isotropic free-space $B$ must not automatically be equated to the coefficient for a specified $z$-polarized field.

For hydrogen, take the quantization axis along $z$, neglect spin-orbit coupling, and assume perfect plates, a wide in-plane region and an unmodified atomic wavefunction: $a_{\mathrm{B}}\ll d\ll c/{\omega }_0$, with negligible surface-induced mixing or shifts. The electric-dipole selection rules for hydrogen require $\Delta l=\pm 1$; the allowed $z$ field has $\Delta m_{\ell }=0$. Hence the polarization-selective spontaneous emission between conducting plates givesThe thin-cavity enhancement of a normal electric dipole applies: the $2p_0\to 1s$ dipole points along $z$ and couples to the enhanced mode density. For $m_{\ell }=\pm 1$, the transition dipoles lie in the $x$–$y$ plane and couple to none of these low-frequency modes: the electric-dipole decay rate is zero in the ideal model, so this channel's lifetime is infinite. Real finite, imperfect plates and additional decay or mixing channels limit the lifetime. The order-one orientation factor for the allowed transition does not change the requested lifetime scaling.

The time-independent Schrödinger equation is $[-{\hslash }^2{\nabla }^2/(2m)+V]\psi =E\psi$, with attractive Coulomb potential $V(r)=-\kappa /r$, where $\kappa =e^2/(4\pi {\epsilon }_0)$. Separating $\psi =R(r)Y_{\ell }^m(\theta ,\phi )$ uses the spherical harmonic angular eigenvalue $-\ell (\ell +1)$ of the unit-sphere Laplacian. The radial kinetic contribution is $-{\hslash }^2(R^{\prime \prime }+2R^{\prime }/r)/(2m)$, the angular kinetic contribution is the centrifugal term ${\hslash }^2\ell (\ell +1)R/(2m{r}^2)$, and the remaining term is the attractive potential energy. The right side is the energy eigenvalue times the radial wavefunction. Here the stated $m$ neglects nuclear recoil; including it replaces the electron mass by the reduced mass.

For $\ell =0$, substitution of the ground-state exponential givesIts $1/r$ coefficient must vanish and its constant coefficient determines the energy, soHere $a_0={\hslash }^2/(m\kappa )$ is the Bohr radius.

For $R_2=N_2(r+b)e^{-\beta r}$, direct differentiation yieldsCancel the nonzero exponential in the radial Schrödinger equation and compare coefficients of $r$, the constant term, and $1/r$. They give, respectively,ConsequentlyThe positive decay constants ensure normalizability; the second radial wavefunction has one positive-radius node at $2a_0$, as appropriate to the first radial excitation.

If the entire energy gap is carried by one photon, neglecting atomic recoil, conservation of energy gives the requested frequencyThere is a physical qualification: these are the $2s$ and $1s$ states, so the usual single-photon electric-dipole transition is forbidden by the electric-dipole selection rules for hydrogen. Explicitly, both angular factors are $Y_0^0$, and $\int |Y_0^0{|}^2\hat{\mathbf{r}}d\Omega =0$, so every component of $⟨1s|\mathbf{r}|2s⟩$ vanishes. The leading isolated-atom decay is instead two-photon emission, for which ${\nu }_1+{\nu }_2={\nu }_{\mathrm{gap}}$ and individual frequencies are not fixed. This metastability and the two-photon channel are documented in NIST's hydrogen spectral-data compilation. Thus the boxed answer is the energy-gap frequency under the printed single-photon assumption, rather than an assertion of an allowed electric-dipole line.

In position representation,which differentiates only with respect to $x$ and $y$. Multiplication by $z$ therefore commutes with it:Taking the matrix element of this commutator between angular-momentum eigenstates givesThus the matrix element can be nonzero only whenThis is the magnetic part of the electric-dipole selection rules for hydrogen.

Insert hydrogen energy eigenstates on either side of the commutator. Because $L_z$ is Hermitian and has eigenvalue $\hslash m$,ThusThis is a necessary electric-dipole selection rule, not a sufficient condition for a nonzero matrix element. For example, $⟨200|z|200⟩=0$ by parity even though $m=m^{\prime }=0$. The angular factor $z=r\cos \theta$ additionally requires $l^{\prime }=l\pm 1$: multiplication of a spherical harmonic by $\cos \theta$ gives only harmonics with the same $m$ and adjacent $l$. The commutator alone establishes only the magnetic quantum number restriction; radial integrals and the remaining electric-dipole selection rules for hydrogen must still be considered.

An electric field shifts and can split the energy eigenvalues of an atom. This is the Stark effect; its hydrogen atom ground-state case is quadratic in a weak field.

The observable in Stark effect spectroscopy is a change in a spectral line, rather than a direct reading of an individual energy eigenvalue. If an upper energy eigenstate $u$ emits a photon into a lower energy eigenstate $l$, the Planck constant $h$ relates its frequency to the difference:Here $\mathcal{E}$ denotes the applied electric field component along a chosen axis. Both levels can move, and electric-dipole selection rules for hydrogen decide which pairs produce observable spectral lines. This makes Stark effect spectroscopy a probe of energy eigenstates and their electric dipole moments: the slope $-\partial E/\partial \mathcal{E}$ is the corresponding dipole component by the Hellmann–Feynman theorem. The comparison with Zeeman splitting is useful: there an applied magnetic field supplies the perturbation.

The even, spherically symmetric hydrogen atom ground state has no permanent electric dipole, so a uniform electric field gives no first-order energy shift. The electric-dipole selection rules for hydrogen allow odd-parity excited states to mix in at second order, yielding a negative shift quadratic in the field.

Here there is a nondegenerate energy eigenvalue, so second-order nondegenerate perturbation theory applies. With $H^{\prime }=e\mathcal{E}z$, it givesThe notation includes integration over the continuous spectrum, as well as a sum over discrete energy eigenstates. All denominators are negative because $1s$ is the ground state. The positive electric polarizability ${\alpha }_{1s}$ therefore lowers its energy.^[ref]

An independent way to see the coefficient avoids truncating that sum. Define $E_{\mathrm{h}}=e^2/(4\pi {ϵ}_0{a}_0)$ and $f=e{a}_0\mathcal{E}/E_{\mathrm{h}}$. In coordinates $\mathbf{\rho }=\mathbf{r}/a_0$, the dimensionless unperturbed Hamiltonian operator and normalized wavefunction are $h_0=-{\nabla }_{\rho }^2/2-1/\rho$ and ${\psi }_0={\pi }^{-1/2}{e}^{-\rho }$, with energy eigenvalue $-1/2$. Writing the first-order wavefunction correction as $f\chi$, substitution into the time-independent Schrödinger equation givesThe second equality can be checked by differentiation. Its parity makes $\chi$ orthogonal to ${\psi }_0$. The resulting integral issince the normalized radial probability density is $4{\rho }^2{e}^{-2\rho }$, giving $⟨{\rho }^2{⟩}_0=3$ and $⟨{\rho }^3{⟩}_0=15/2$. Converting back to SI units gives the stated electric polarizability. The induced electric dipole moment is $-\partial \Delta E/\partial \mathcal{E}={\alpha }_{1s}\mathcal{E}$ and tends to zero with the electric field, unlike the selected degenerate branches' leading dipoles. Both calculations describe weak-field level shifts; a spatially uniform static electric field also allows eventual quantum tunnelling and ionization, which these real energy corrections do not calculate.