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Updated: Jun 18, 2026
Analysis of Complex Molecules and Their Reactions on Surfaces by Means of Cluster-Induced Desorption/Ionization Mass Spectrometry
Published on: March 1, 2020
Valence ionization spectra of group six metal hexacarbonyls studied by the symmetry-adapted cluster-configuration
Ryoichi Fukuda1, Seigo Hayaki, Hiroshi Nakatsuji
1Quantum Chemistry Research Institute, JST CREST, Kyodai Katsura Venture Plaza, North building, 36-1 Goryo Oohara, Nishikyo-ku, Kyoto 615-8245, Japan. fukuda@qcri.or.jp
Abstract:
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.
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