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 gives the electric-dipole interaction , which is odd under reflection. Hence
since 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 to , 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 , 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: is even, while is odd. The first-order nondegenerate perturbation theory correction is consequently
The electric field does mix opposite-parity quantum states, and second-order nondegenerate perturbation theory contains two factors of . Its leading contribution is thus proportional to : this is a quadratic Stark effect. More generally, applying the parity operator changes into , so their corresponding energy eigenvalues agree. An analytic expansion about zero electric field contains only even powers of . We assume is small compared with the unperturbed excitation scale.