 Zeeman populations from an unpolarized angular-momentum multiplet

An equal incoherent mixture within a fixed total-$J$ multiplet has density operator $\rho =P_J/(2J+1)$, where $P_J$ is its orthogonal projection. If the applied-field Hamiltonian operator is proportional to $L_z+2S_z$ and no spin-orbit interaction is retained, its energy eigenstates are the uncoupled states $|m_L,m_S⟩$. The Born rule gives their populations by the formula above, or equivalently by squared Clebsch-Gordan decomposition coefficients. Equal populations of coupled states need not give equal populations of magnetic energy eigenvalues.

For $L=1,S=1/2,J=3/2$, the nonextremal coupled states have weights $2/3$ and $1/3$ in their two uncoupled components. The five dimensionless magnetic energies $-2,-1,0,1,2$ then have populations $1/4,1/6,1/6,1/6,1/4$; the zero energy contains two independent states, each with population $1/12$. In a different, weak-field approximation with a dominant spin-orbit interaction, projecting into the isolated multiplet gives the Landé g-factor spectrum instead. The full operator and its projection must not be interchanged.