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The Stark effect changes atomic energy levels in a static electric field. For $\mathbf{E}=\mathcal{E}\hat{\mathbf{z}}$, the electric-dipole interaction is $H^{\prime }=-d_z\mathcal{E}=e\mathcal{E}z$ for an electron, with $e>0$. A nondegenerate state of definite parity has $⟨z⟩=0$, so its leading quadratic Stark effect isThe ground state shift is negative, conventionally $-\alpha {\mathcal{E}}^2/2$ with positive electric polarizability.^[ref]

Degenerate opposite-parity states require degenerate perturbation theory. In ideal Coulomb hydrogen, the $2s,2p_0$ subspace has an off-diagonal matrix element of magnitude $3e{a}_{\mathrm{B}}\mathcal{E}$, where $a_{\mathrm{B}}$ is the Bohr radius. Its mixed states shift byThis Linear Stark effect in the first excited hydrogen eigenspace assumes fine-structure and Lamb splittings are negligible compared with the mixing. In an isolated parity eigenstate with such degeneracies resolved, sufficiently weak fields restore quadratic behaviour. Strong fields require further mixing and can ionize the atom.^[ref]

For a bound energy eigenstate with a nondegenerate energy eigenvalue of an even one-dimensional potential, the wavefunction can be chosen with definite parity. A uniform electric field $\mathcal{E}$ gives the electric-dipole interaction $H^{\prime }=-q\mathcal{E}x$, which is odd under reflection. Hencesince $x|{\psi }_n(x){|}^2$ is odd. Second-order nondegenerate perturbation theory then gives the leading allowed Stark effect shift:Only opposite-parity intermediate states have nonzero position matrix elements. More generally, reflection maps $H(\mathcal{E})$ to $H(-\mathcal{E})$, so an analytic nondegenerate energy level is an even function of the field. This explains the absence of all odd orders and the usual quadratic Stark effect.

A level separation changes by the difference of the two quadratic coefficients. Symmetry alone does not guarantee a nonzero differential shift: in a displaced quantum harmonic oscillator every level moves by the same $-q^2{\mathcal{E}}^2/(2m{\omega }^2)$, leaving every spacing unchanged. Degenerate states would instead require degenerate perturbation theory and can split linearly; the nondegeneracy of one-dimensional bound states applies to ordinary isolated well levels.

The unperturbed infinite square well is invariant under the parity operator. Its one-dimensional energy eigenvalues are nondegenerate, so each energy eigenstate has definite parity. Its position expectation value therefore vanishes: $|{\varphi }_n(x){|}^2$ is even, while $x$ is odd. The first-order nondegenerate perturbation theory correction is consequentlyThe electric field does mix opposite-parity quantum states, and second-order nondegenerate perturbation theory contains two factors of $eEx$. Its leading contribution is thus proportional to $E^2$: this is a quadratic Stark effect. More generally, applying the parity operator changes $H(E)$ into $H(-E)$, so their corresponding energy eigenvalues agree. An analytic expansion about zero electric field contains only even powers of $E$. We assume $e|E|a$ is small compared with the unperturbed excitation scale.