Past exam of the quantum, atomic and molecular physics course of the University of Oxford / 2016 / 1 / a / Solution

Potassium has a closed 18-electron core and one valence electron. In $3d{}^2{D}_{5/2}$ the orbital label specifies principal quantum number $n=3$ and single-electron orbital angular momentum $l=2$. The term letter D specifies total orbital angular momentum $L=2$, the superscript $2S+1=2$ specifies $S=1/2$, and the subscript is total electronic angular momentum $J=5/2$. The $5p{}^2{P}_{3/2}$ state instead has $n=5$, $l=L=1$, the same spin, and $J=3/2$. The closed electron shell that forms the core contributes no net $L$ or $S$ in this alkali-like approximation. The dash identifies a pair of levels rather than by itself specifying the direction of emission.

The leading electric dipole transition rules for one active electron areThe electronic parity must change, since the electric dipole operator is odd under spatial reflection. The electric-dipole selection rule imposes no general restriction on changing $n$ by more than one. The rule for magnetic sublevels depends on the radiation's polarization relative to the quantization axis: the $q=0$ component couples equal $m_J$, whereas $q=\pm 1$ supplies the other changes. In a many-electron description using LS coupling the total orbital rule is $\Delta L=0,\pm 1$, excluding $L=0\leftrightarrow 0$; for a single active electron the stronger $\Delta l=\pm 1$ applies. Thus the displayed D–P pair satisfies the leading rules. Relativistic mixing and higher-multipole transitions can permit weaker lines outside the approximation of electric dipole transitions.