On the sodium D line emission in the terrestrial nightglow

Emission from atomic Na, consisting of a doublet of lines at 589.0 and 589.6 nm, is a prominent feature of the earth’s nightglow. A large data-base of measurements of the relative intensities of the D lines (RD) was gathered at three locations: the ALOMAR observatory, Andenes (Norway, 69°N), Kuujjuarapik (Canada, 55°N) and the Danum Valley (Borneo, 8°N). RD varies between 1.5 and 2.0, with an average value of 1.67. These results were interpreted using a theoretical model of the Na nightglow which involves initial production of electronically excited NaO(A2Σ) from the reaction between Na and O3, followed either by reaction with O to generate Na(2PJ) with a branching ratio of 1/6 and a J=3/2 to 1/2 propensity of 2.0, or quenching of NaO(A) to NaO(X2Π) by O2. The resulting NaO(X) then reacts with O to generate Na(2PJ) with a branching ratio of 1/6 and a J=3/2 to 1/2 propensity of 1.5. These branching ratios and spin-orbit propensities are derived from statistical correlation of the electronic potential energy surfaces connecting the reactants NaO(A)+O and NaO(X)+O with the products Na+O2, through the Na+O2− ion-pair intermediate. A fit of this statistical model to the results of an earlier laboratory study (Slanger et al., 2005), where RD was measured as a function of the ratio [O]/[O2], indicates that the rate coefficient for the quenching of NaO(A) by O2 is around 1×10−11 cm3 molecule−1 s−1. The statistical model is also in good accord with recent high resolution observations of the Na D line widths ( Harrell et al., 2010). An atmospheric model is then used to show that gravity wave-driven perturbations to the Na layer can account for the observed variability of RD.

► Extensive set of measurements of the Na D line ratio in the nightglow. ► Show that the average ratio is 1.67, and that it ranges from 1.5 to 2.0. ► Provide the first theoretical explanation for the spin-orbit propensities in the reactions of NaO(A) and NaO(X) with O.