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Published November 1, 1973 | Published
Journal Article Open

Theoretical and Experimental (Electron-Impact) Studies of the Low-Lying Rydberg States in O2


Theoretical studies of the n=3,4,and 5 Rydberg series in O2, converging to O2+(X 2Πg), are presented and correlated with electron energy-loss spectra of molecular oxygen, in the region from 7.0 to 10.5 eV. The energy-loss spectra have been studied as a function of the scattering angle for a incident electron energy of 45 eV. The angular dependence determined for various features in the energy-loss spectra have been correlated with the known behavior for transitions between electronic states of certain symmetry, and with the theoretical results, to identify the low-lying Rydberg states. Four vibrational levels of the (3s σg) 3Πg Rydberg state have been observed superposed on top of the maximum intensity portion of the Schumann-Range continuum with T00=8.145±0.020 eV. The theoretical results, combined with the energy-loss measurements and the high-resolution photon-absorption work, lead to the assignment of the lowest dipole-allowed 3Σu- and 3Πu Rydberg states at T00≤9.31 eV and T00=9.97 eV, respectively.

Additional Information

©1973 The American Physical Society. Received 14 May 1973. The authors would like to thank M. Ogawa and K.R. Yamawaki of USC and L. Sanche and G.L. Schulz of Yale for providing the results of their work prior to publication. The cooperation of D. Albritton of NBS-Boulder in providing the spectroscopic data of O2 and O2^+ prior to publication was greatly appreciated. Stimulating conversations with Thom Dunning of Caltech, Y. Tanaka of AFCRL, and M. Ogawa of USC were helpful in formulating the interpretation presented in this paper. The excellent computational help of N.A. Fiamengo of Aerospace in the analysis of the experimental data is gratefully acknowledged. [W.A.G.'s] work partially supported by USAF SAMSO Contract F04701-72-C-0172 to The Aerospace Corporation; the Caltech President's Fund (PF-103); and NASA Contract No. NAS7-100 to JPL. [W.A.G. was] partially supported by Grant (GP-15423) from the NSF. Arthur A. Noyes Laboratory for Chemical Physics Contribution No. 4670. [W.J.H. was an] NDEA Fellow.

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