The 1650-1350 Å absorption spectrum of nitrogen dioxide
An analysis of the 1650-1350 Å band system of nitrogen dioxide has been carried out. A pattern of band spacings and intensities is found that is complex but regular. It is shown that this pattern is qualitatively, and to a large extent quantitatively, just what would be expected for a transition in which the shape of the molecule changes from bent to linear. The transition is a parallel one and the upper state has 2 Σ + u symmetry. The symmetrical stretching frequency is increased from its ground-state value to ca. 1420 cm -1 in the upper state. The upper-state bending frequency is ca. 600 cm -1 . The N — O length is decreased from its groundstate value, probably to 1·1(3) Å. The upper state resembles closely the ground state of NO + 2 . The transition is to be classed as one of the Rydberg transitions leading to the first ionization potential of NO 2 ; and the orbital to which the odd electron is transferred in the transition is (pσ) in type. The anharmonic constant g 22 for the linear upper state is found to be 2·(3) cm -1 . Other Rydberg transitions may well be present in the region, but have not been definitely identified.