Electronic states of ketene

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30 Citations (Scopus)

Abstract

State of the art ab initio techniques of molecular electronic structure theory have been employed to investigate different structural aspects of the electronic states of ketene. Vertical excitation energies of more than 40 singlet and triplet states have been determined from equation-of-motion coupled cluster singles and doubles (EOM-CCSD) and configuration interaction singles (CIS) calculations employing extended basis sets. Most importantly, all singlet and triplet electronic states below 70 000 cm-1, close to the first ionization potential of ketene, 77 500 cm-1 have been determined. Only four pure excited valence states have been identified: the 1 3A1, 2 3A1, 1 3A2, and 1 1A2 states. Vertical ionization energies have also been determined at the EOM-CCSD level. They are found to be in nice accord with the available experimental results. All lower-lying members of the Rydberg series of ketene terminating at 77 500 cm-1 are assigned based on theoretical data, symmetry considerations, and use of the Rydberg formula and the available experimental results. High-quality estimates are given for the possible occurrence of fluorescence emission from the first singlet state of ketene.

Original languageEnglish
Pages (from-to)1034-1045
Number of pages12
JournalThe Journal of Chemical Physics
Volume105
Issue number3
Publication statusPublished - Jul 15 1996

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Electronic states
equations of motion
Rydberg series
Ionization potential
molecular electronics
electronics
stopping
ionization potentials
configuration interaction
atomic energy levels
Equations of motion
occurrences
electronic structure
valence
Molecular electronics
ionization
fluorescence
energy
Excitation energy
symmetry

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

Electronic states of ketene. / Szalay, P.; Császár, A.; Nemes, L.

In: The Journal of Chemical Physics, Vol. 105, No. 3, 15.07.1996, p. 1034-1045.

Research output: Contribution to journalArticle

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