Computational Chemistry and Molecular Modeling
Atomic, Molecular and Optical Physics
Wiley InterScience Backfile Collection 1832-2000
Chemistry and Pharmacology
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 → Vσ(σ → σ*) intravalence contributions to photoexcitation and ionization spectra in CO and H2CO 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.
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