Hydrogen energy eigenbasis

Neglecting spin, bound hydrogen eigenstates are labelled $|n,\ell ,m⟩$, where $\ell =0,\dots ,n-1$ and $m=-\ell ,\dots ,\ell$. Their unperturbed energy depends only on $n$.

Neglecting spin, the hydrogen level with principal quantum number $n$ has degeneracy

For the $z$ component of position,requires $\Delta m=0$ and $\Delta \ell =\pm 1$. The first condition follows from $[L_z,z]=0$; the second follows from the vector-operator angular-momentum relation together with odd parity.

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

The $n=2$ eigenspace has basis

A perturbation $g{L}^2$ preserves the hydrogen eigenbasis and shifts $|n,\ell ,m⟩$ byIn the first excited eigenspace, the $2s$ state is unshifted and the three $2p$ states receive the common shift $2g{\hslash }^2$.

The operators $X_3$ and $P_3$ commute with $L_3$, so they preserve $m$. Both are odd under parity, so they connect only states of opposite orbital parity. Within the $n=2$ eigenspace, only the pair $|2,0,0⟩$ and $|2,1,0⟩$ can therefore have nonzero matrix elements.

Forset $a=U(t)b$ withThen $b$ evolves under the constant Hamiltonian