N(2) band oscillator strengths at near-threshold energies

Band oscillator strengths for 58 bands in the near-threshold region of N(2), i.e., from 116 200 to 125 400 cm(-1), are derived from measured band-integrated optical depths. The complexity of the absorption spectrum demands that the measurements be carried out on rotationally cold supersonic jet expansions. The column density N in the absorbing path of the jet cannot be measured directly. Instead, the room temperature f values of selected calibration bands are used to convert the band-integrated optical depths of the jet-cooled calibration bands to preliminary column densities [N], which, plotted as a function of jet reservoir pressure p, scatter around a straight line passing through the origin of the graph. From the slope of the line, first estimates of the effective column density N can be derived for any value of p. Second estimates are obtained by repeating the same procedure using ab initio calculated f values based on the work of Spelsberg and Meyer [J. Chem. Phys. 115, 6438 (2001)]. Depending on the jet configuration, the two estimates differ by 3%-15%; their average is accepted as the best approximation to N. The derived band oscillator strengths are compatible with ab initio results of Spelsberg and Meyer and reproduce the observations reasonably well, even where two or more transitions combine in the formation of complex band structures. They also clarify the analysis of the absorption spectrum in the region of the 7p(0) complex [Jungen, Huber, Jungen, and Stark, J. Chem. Phys. 118, 4517 (2003)] and lead to a plausible interpretation of the spectrum in the 124 680-124 880 cm(-1) range. As a result, the lowest three vibronic levels of both the 3(')d(')sigma and the 4(')s(')sigma core excited states have now been identified.