Comment on: Observation of Strong Rydberg-Valence Mixing in the E (3) Sigma (u) (-) State of O2 by 3+1 Multiphoton Ionization Photoelectron Spectroscopy
AIR FORCE GEOPHYSICS LAB HANSCOM AFB MA
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A recent paper on the 3 1 MPI photoelectron spectrum of O2 via it s E 3 Sigma u- state shows that the so-called longest band has a strongly mixed Rydberg-valence character. To prevent confusion it should be noted that this E state was relabeled B 3 Sigma u- because of this mixture and its formation from the upper state of the well known Schumann-Runge bands namely, B 3 Sigma u-. Based on theoretical calculations, the B 3 Sigma u- state was predicted to have as its first three vibrational levels, the longest, second, and third bands at 1244, 1206, and 1172 A. Also show that their MPI data agree with the longest being a 0,0 band which they report is in contrast to the original assignment who assigned it as 1,0. It is necessary to point out that the original assignment was changed on the basis of a reanalysis of the spectroscopic data. The longest, second, and third bands should indeed be the 0,0, 1,0, and 2,0 bands of the B 3 Sigma u- -X 3 Sigma g- transition. More recent work on the O2 absorption spectrum at high temperature supports these vibrational assignments. Reprints.
- Atomic and Molecular Physics and Spectroscopy