Spectral properties of minimal-basis-set orbitals: Implications for molecular electronic continuum states

Early studies of the electronically excited states of molecules by John A. Pople and coworkers employing ab initio single‐excitation configuration interaction (SECI) calculations helped to simulate related applications of these methods to the partial‐channel photoionization cross sections of polyato...

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Bibliographic Details
Published in:International journal of quantum chemistry 2005, Vol.102 (5), p.948-955
Main Authors: Langhoff, P. W., Winstead, C. L.
Format: Article
Language:English
Subjects:
continuum orbitals
excited states
molecular photoionization
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Summary:Early studies of the electronically excited states of molecules by John A. Pople and coworkers employing ab initio single‐excitation configuration interaction (SECI) calculations helped to simulate related applications of these methods to the partial‐channel photoionization cross sections of polyatomic molecules. The Gaussian representations of molecular orbitals adopted by Pople and coworkers can describe SECI continuum states when sufficiently large basis sets are employed. Minimal‐basis virtual Fock orbitals stabilized in the continuous portions of such SECI spectra are generally associated with strong photoionization resonances. The spectral attributes of these resonance orbitals are illustrated here by revisiting previously reported experimental and theoretical studies of molecular formaldehyde (H2CO) in combination with recently calculated continuum orbital amplitudes. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005
ISSN:0020-7608
1097-461X
DOI:10.1002/qua.20455