 Weak-field Zeeman splitting

Use the leading nonrelativistic magnetic coupling for an electronic level with total angular momentum operator $\mathbf{J}$, and choose the $z$ axis along a uniform external magnetic field $\mathbf{B}=B\hat{\mathbf{z}}$, $B\ge 0$. Write its magnetic quantum number as $m_J$, so $J_z|J,m_J⟩=\hslash m_J|J,m_J⟩$. There are $2J+1$ possibilities from $-J$ to $J$. With Landé g-factor $g_J$, the first-order shift isHere $e>0$ is the magnitude of the Electron electric charge, $m_e$ its mass, $h$ the Planck constant, and ${\mu }_B$ the Bohr magneton. Both $g_J$ and $m_J$ are dimensionless; with $B$ measured in tesla and ${\mu }_B$ in joules per tesla, $\Delta E$ is in joules. The photon frequency shift $\Delta {\nu }_{ul}$ is in hertz, not angular frequency; indices $u,l$ denote upper and lower levels. NIST states this weak-field convention and its orbital/spin assumptions explicitly.^[ref]

The sign follows directly from magnetic dipole potential energy. Within this electronic $J$ multiplet, the projected magnetic dipole moment is $\mathbf{\mu }=-g_J{\mu }_B\mathbf{J}/\hslash$. Therefore $H_Z=-\mathbf{\mu }\cdot \mathbf{B}$ has the displayed positive coefficient. Subtracting the shifts of the two levels and using photon energy $h{\nu }_{ul}=E_u-E_l$ gives the transition formula. For the orbital case, ${\mu }_B/h=e/(4\pi m_e)$ gives the same leading frequency spacing as the classical charged oscillator. This explains the historical sensitivity to charge divided by mass; the quantum state derivation here is modern.

“Weak” compares interaction energies: mixing with neighbouring fine structure levels must be small, so $J$ remains a useful quantum number. The formula keeps the term linear in $B$ and neglects quadratic shifts. It also omits hyperfine structure; if that is resolved and controls the coupling, the appropriate total electronic-plus-nuclear angular momentum and splitting factor must replace $J,g_J$. Weak compared with fine structure does not automatically mean weak compared with hyperfine structure.