Level sequence and splitting identification of closely-spaced energy levels by angle-resolved analysis of the fluorescence light

The angular distribution and linear polarization of the fluorescence light following the resonant photoexcitation is investigated within the framework of the density matrix and second-order perturbation theory. Emphasis has been placed on "signatures" for determining the level sequence and splitting of intermediate (partially) overlapping resonances, if analyzed as a function of the photon energy of the incident light. Detailed computations within the multiconfiguration Dirac-Fock method have been performed especially for the $1s^{2}2s^{2}2p^{6}3s\;\, J_{i}=1/2 \,+\, \gamma_{1} \:\rightarrow\: (1s^{2}2s2p^{6}3s)_{1}3p_{3/2}\;\, J=1/2, \, 3/2 \:\rightarrow\: 1s^{2}2s^{2}2p^{6}3s\;\, J_{f}=1/2 \,+\, \gamma_{2}$ photoexcitation and subsequent fluorescence emission of atomic sodium. A remarkably strong dependence of the angular distribution and linear polarization of the $\gamma_{2}$ fluorescence emission is found upon the level sequence and splitting of the intermediate $(1s^{2}2s2p^{6}3s)_{1}3p_{3/2}\;\, J=1/2, \, 3/2$ overlapping resonances owing to their finite lifetime (linewidth). We therefore suggest that accurate measurements of the angular distribution and linear polarization might help identify the sequence and small splittings of closely-spaced energy levels, even if they can not be spectroscopically resolved.