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AbstractAbstract
[en] Theoretical studies in the intensity-borrowing sudden approximation are reported of inner-valence-shell photoionization cross sections in N2 and CO. The required ionic-state energies and spectroscopic amplitudes are obtained from appropriate Green's-function and configuration-interaction calculations, and previously devised Stieltjes-Tchebycheff moment-theory techniques are employed in determinations of corresponding continuum dipole transition moments in the static-exchange approximation. Comparisons are made of the Green's-function calculations in the two-particle-hole Tamm-Dancoff approximation with wavefunction results obtained from single-excitation and polarization configuration-interaction calculations. Detailed descriptions are given of the calculated spectroscopic intensity distributions and of the hole-particle configurational compositions of the corresponding inner-valence-shell ionic states, and comparisons are made with previously reported wavefunction studies in N+2 and CO+. Spectroscopic assignments are suggested on basis of the present calculations for the strong features observed recently in higher-resolution inner-valence-shell photoelectron spectra. The corresponding calculated partial-channel photoionization cross sections for the designated C2 Σ+sub(u), F 2Σ+sub(g), G 2Σ+sub(g), and (2sigma-1sub(g)) 2Σ+sub(g) bands in N2 and C 2Σ+, D 2PI, F 2Σ+, G 2Σ+, and (3sigma-1) 2Σ+ bands in CO are found to be in good quantitative accord with dipole (e,2e), (e,e + ion), and synchrotron-radiation studies. (orig.)
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Journal Article
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Chemical Physics; ISSN 0301-0104;
; v. 58(1); p. 71-91

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