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Stieltjes orbitals for molecular photoexcitation and ionization spectra: N → V σ and N → V π resonance features in CO and H 2 CO cross sections
Author(s) -
Hermann M. R.,
Diercksen G. H. F.,
Fatyga B. W.,
Langhoff P. W.
Publication year - 1984
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560260864
Subject(s) - photoionization , photoexcitation , molecular orbital , atomic physics , molecular orbital theory , complete active space , linear combination of atomic orbitals , chemistry , excited state , atomic orbital , ionization , spectral line , physics , molecular physics , quantum mechanics , molecule , electron , ion
Abstract Computational studies are reported of Stieltjes orbitals for Hilbert‐space descriptions of discrete and continuum molecular electronic eigenstates. Particular attention is focused on the identification of N → V π (π → π*) and N → V σ (σ → σ*) intravalence contributions to photoexcitation and ionization spectra in CO and H 2 CO molecules. Three‐dimensional graphical representations of appropriate Stielties orbitals serve to identify the σ → σ* transitions of Mulliken as photoionization resonances above threshold in these compounds, whereas the corresponding π → π* contributions are spectrally localized as familiar discrete excited states. The development illustrates the nature and properties of Stieltjes orbitals, and demonstrates their utility in studies of both discrete and continuum excitation spectra on a common basis.