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Photoexcitation and ionization in molecular oxygen: Theoretical studies of electronic transitions in the discrete and continuous spectral intervals

Gerwer, A. and Asaro, C. and McKoy, B. V. and Langhoff, P. W. (1980) Photoexcitation and ionization in molecular oxygen: Theoretical studies of electronic transitions in the discrete and continuous spectral intervals. Journal of Chemical Physics, 72 (1). pp. 713-727. ISSN 0021-9606. doi:10.1063/1.438908.

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Theoretical studies of valence-electron (1πg, 1πu, 3σg) photoexcitation and ionization cross sections in molecular oxygen are reported employing separated-channel static-exchange calculations and the Stieltjes–Tchebycheff moment-theory technique. As in previously reported investigations of photoexcitation and ionization in small molecules following this approach, canonical Hartree–Fock orbitals, large Gaussian basis sets, and many-electron eigenstates of correct symmetry are used in defining appropriate noncentral static-exchange potentials and in computations of the appropriate discrete and continuum transition strengths. It is particularly important in molecular oxygen to incorporate the appropriate ionic parentages of the various photoionization multiplet states in order to obtain the correct partial-channel cross sections. The calculated discrete series associated with 1πg excitation are found to be in good agreement with available experimental assignments and previously reported theoretical studies, and the predicted states associated with 1πu and 3σg excitations are in general accord with assignments for the higher series based on spectral and quantum-defect analysis. Although the observed photoelectron spectra and photoionization cross sections are relatively complex, the calculated total vertical electronic photoabsorption cross section and the partial-channel photoionization cross sections for production of X 2πg, a 4πu, A 2πu, 2 2πu, 3 3IIu, b 4∑g-, and B 2∑g-, ionic states are found to be in good accord with recent synchrotron radiation, line-source, electron-impact, and (e,2e) dipole oscillator-strength measurements when proper account is taken of the parentages of the various multiplet states. The partial-channel cross sections exhibit resonancelike structures that can be attributed to contributions from diabatic valencelike virtual states that appear in the appropriate photoionization continua, rather that in the corresponding discrete spectral intervals. These features in the dipole spectrum of molecular oxygen are discussed and are contrasted and compared with the results of previously reported related studies in molecular nitrogen and carbon monoxide.

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Additional Information:© 1980 American Institute of Physics. Received 16 April 1979; accepted 27 April 1979. The authors thank C.E. Brion and M.J. Van der Wiel for kindly making the results of their experimental studies available prior to publication, and for helpful correspondence. We also thank R.L. Blake for permission to cite his experimental results prior to publication, and A.U. Hazi for his help in clarifying the origins of the four 1πμ cross sections. Acknowledgement is made to the National Science Foundation for support provided to B.V.M., and to the Donors of the Petroleum Research Fund, administered by the American Chemical Society, and to the National Research Council, for providing support to P.W.L. The kind hospitality of J.O. Arnold and S.R. Langhoff of the NASA-Ames Research Center Computational Chemistry Group, and of D. Bershader of the Department of Aeronautics and Astronautics, Stanford University, to P.W.L. is also gratefully acknowledged.
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Petroleum Research FundUNSPECIFIED
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ID Code:12058
Deposited By: Tony Diaz
Deposited On:24 Oct 2008 06:22
Last Modified:08 Nov 2021 22:25

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