New Rydberg series of NO₂in the region 500 to 800 AA

Some remarks on the photodynamics of NO2

“…Of these states, those converging on the linear ground (1) 1 S + electronic state of the cation (also labelled (1) 1 A 1 in C 2v symmetry) have received the most attention due to their accessibility in the laboratory; although other excited valence states 38,96,97,122 and Rydberg series that converge on excited ion states also exist. 38,123,124 A strong series of overlapping absorption bands are observed between 6.4 and 9.5 eV in the electron impact spectra recorded by Edqvist and co-workers 123 and Au and Brion. 38 Nakayama et al detected the same absorption profile with higher resolution using single photon optical spectroscopy.…”

“…The overlapping vibronic progressions of these Rydberg series and the ion continua to which they converge characterise the absorption spectrum of NO 2 between 9.5 and 20 eV. 38,96,123,124 In this excitation range, seven or more ion states can be accessed. Here the density of ion states is due to the doublet ground state structure of neutral NO 2 .…”

“…This feature was attributed to the 3p ' 1b 1 and 3ss ' 5a 1 transitions by Au and Brion, although vibrationally resolved signatures of these Rydberg states have yet to be identified. At excitation energies between 14.3 and 18.5 eV Rydberg series corresponding to the excitation of the 3b 2 valence electron and converging on the (2) 3 B 2 ion state (with a T 0 of B18.860 eV 124,138,140,141 ) are said to dominate the absorption profile. 38,123,124,140 These Rydberg series were originally studied by Tanaka and Jursa 140 where they observed four series with different quantum defects.…”

“…At excitation energies between 14.3 and 18.5 eV Rydberg series corresponding to the excitation of the 3b 2 valence electron and converging on the (2) 3 B 2 ion state (with a T 0 of B18.860 eV 124,138,140,141 ) are said to dominate the absorption profile. 38,123,124,140 These Rydberg series were originally studied by Tanaka and Jursa 140 where they observed four series with different quantum defects. Using the profile of the strong (2) 3 B 2 photoelectron band, 123,138,141,152 signatures of the different nll ' 3b 2 states have been assigned to peaks occurring between 15.382 eV and the ionisation limit.…”

“…Using the profile of the strong (2) 3 B 2 photoelectron band, 123,138,141,152 signatures of the different nll ' 3b 2 states have been assigned to peaks occurring between 15.382 eV and the ionisation limit. 124 Many of these Rydberg series display vibrational progressions with B0.135 eV spacings which corresponds to the (2) 3 B 2 state symmetric stretch harmonic frequency. 138,141 The common ionisation limit of all these series allows quantum defect values for the different series to be reliably determined, facilitating the assignment of the orbital angular momentum and its projection for each series.…”