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Valence ionization spectra of group six metal hexacarbonyls studied by the symmetry-adapted cluster-configuration interaction method

J. Chem. Phys. 131, 174303 (2009); doi:10.1063/1.3257963

Published 2 November 2009

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Ryoichi Fukuda,1,2 Seigo Hayaki,2 and Hiroshi Nakatsuji1,2
1Quantum Chemistry Research Institute, JST CREST, Kyodai Katsura Venture Plaza, North building, 36-1 Goryo Oohara, Nishikyo-ku, Kyoto 615-8245, Japan
2Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Kyoto-Daigaku-Katsura, Nishikyo-ku, Kyoto 615-8510, Japan
The valence ionization spectra up to 20 eV of group six metal carbonyls, chromium hexacarbonyl, molybdenum hexacarbonyl, and tungsten hexacarbonyl were studied by the symmetry-adapted cluster-configuration interaction (SAC-CI) method. The assignments of the spectra are given based on reliable SAC-CI calculations. The relativistic effects including the spin-orbit effects are important for the ionization spectrum of W(CO)6. The relation between the metal-CO distance and ionization energies was examined. The lowest ionization energies of the three metal carbonyls are approximately the same because of the energy dependence of the metal-CO length and relativistic effects. In Cr(CO)6, the Cr–CO interaction significantly increases the lowest ionization energy in comparison with Mo(CO)6 and W(CO)6 because of the relatively short metal-CO bond length. The relativistic effect reduces the lowest ionization energy of W(CO)6 because the effective core potential of 5d electrons is more efficiently screened as a result of the relativistic contraction of the inner electrons. ©2009 American Institute of Physics
History: Received 6 March 2009; accepted 13 October 2009; published 2 November 2009
Permalink: http://link.aip.org/link/?JCPSA6/131/174303/1
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KEYWORDS and PACS

Keywords
PACS
  • 31.15.am
    Ab initio relativistic configuration interaction (CI) and many-body perturbation calculations (atoms and molecules)
  • 33.15.Dj
    Interatomic distances and angles in molecules
  • 31.30.-i
    Corrections to electronic structure of atoms and molecules
  • YEAR: 2009

PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
Publisher:
AIP is a member of CrossRef AIP

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