 Solution

The quoted expansion is nondegenerate perturbation theory for a known isolated eigenstate of a time-independent Hamiltonian. A useful small-mixing condition is $|⟨k|H_1|i⟩|\ll |E_i-E_k|$ for coupled states. First order is a diagonal expectation value; second order describes virtual mixing. A degenerate or nearly degenerate coupled subspace must first be treated by diagonalization there. Symmetry can eliminate terms, and convergence still needs checking. Ground-state second-order shifts are nonpositive because all denominators are negative.^[ref]

For the rotational Stark effect, $H_1=-pE\cos \theta$, where $\theta$ is the polar angle to the field. The source calls it azimuthal, which is inconsistent with this coupling. Rotor states have parity $(-1{)}^J$, while $\cos \theta$ is odd, so every first-order matrix element within one fixed-$J$ manifold vanishes. The $m$ degeneracy therefore causes no first-order splitting.

Only $J\pm 1$ with the same $m$ contribute in second order. Using their energy differences $2BJ$ and $-2B(J+1)$,For $J\ge 1$ this simplifies to the quadratic Stark shift of a polar linear rotor,For $J=0$, only $J^{\prime }=1,m=0$ contributes, with squared angular matrix element $1/3$ and denominator $-2B$:Here $B$ is the rotational energy constant, unlike the magnetic field in Question3.

The unperturbed line gives $B/h=6.08\mathrm{GHz}$. The $J=1$ shifts are $(pE{)}^2/(10B)$ for $m=0$ and $-(pE{)}^2/(20B)$ for $m=\pm 1$. Subtracting the common lower-state shift gives transition shifts $4(pE{)}^2/(15Bh)$ and $7(pE{)}^2/(60Bh)$. Their separation determines the dipole moment from a rotational Stark doublet:The $\mathrm{D}$ unit is the debye. Using external $h=6.62607015\times 10^{-34}\mathrm{J}\mathrm{s}$ and $1\mathrm{D}=3.33564\times 10^{-30}\mathrm{C}\mathrm{m}$ gives $pE/B\simeq 0.0593$, consistent with weak-field perturbation theory. The two shifted frequencies are about $12.165707$ and $12.162497\mathrm{GHz}$; polarization selects $\Delta m=0$ or $\pm 1$. The inferred value is a magnitude; these shifts do not determine the dipole's sign.^[ref][ref]