Dynamical photoionization observables of the CS molecule: The role of electron correlation
- Dipartimento di Scienze Chimiche e Farmaceutiche, Università degli Studi di Trieste, via L. Giorgieri 1, 34127 Trieste (Italy)
- Dipartimento di Scienze Chimiche e Farmaceutiche, Università degli Studi di Ferrara, via Fossato di Mortara 17, 44121 Ferrara (Italy)
Highly correlated calculations are performed on the primary ionic states and the prominent satellite present in the outer valence photoelectron spectrum of carbon monosulfide (CS). Dyson orbitals are coupled to accurate one particle continuum orbitals to provide a correlated description of energy dependent cross sections, asymmetry parameters, branching ratios, and molecular frame photoelectron angular distributions. The comparison with results obtained at the Hartree-Fock and Density Functional Theory level shows the strong sensitivity of these observables to details of the correlation in the bound states. The behaviour of the well characterized satellite state is analyzed in detail, and shows differences from the relevant primary states, revealing the limitations of a simple intensity borrowing mechanism. The results resolve the intensity disagreement with experiment obtained at the level of the sudden approximation.
- OSTI ID:
- 22304522
- Journal Information:
- Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 20 Vol. 140; ISSN JCPSA6; ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
74 ATOMIC AND MOLECULAR PHYSICS
ANGULAR DISTRIBUTION
BOUND STATE
BRANCHING RATIO
CARBON
CROSS SECTIONS
DENSITY FUNCTIONAL METHOD
ELECTRON CORRELATION
HARTREE-FOCK METHOD
MOLECULES
PHOTOELECTRON SPECTROSCOPY
PHOTOIONIZATION
SUDDEN APPROXIMATION