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Published June 15, 1987 | Published
Journal Article Open

The spectroscopy of the group VIb transition metal hexacarbonyls using the electron impact method

Abstract

The electron energy-loss spectra of Cr(CO)6, Mo(CO)6, and W(CO)6 were measured at impact energies of 25, 50, and 100 eV and at scattering angles from 0° to 90°. The differential cross sections (DCS's) were obtained for several features in the 3–7 eV energy-loss region. The symmetry-forbidden nature of the 1A1g → 1A1g,2t2g(π) → 3t2g(π*) transition in these compounds was confirmed. Several low energy excitations were assigned to ligand field transitions on the basis of the energy and angular behavior of their associated DCS's. No transitions which could clearly be assigned to singlet → triplet excitations involving metal orbitals were located in these molecules. In addition, a number of states lying above the first ionization potential were observed for the first time. Several of these excitations seem to correspond quite well to some of the transitions observed in free CO.

Additional Information

© 1987 American Institute of Physics. Received 3 December 1984; accepted 13 November 1986. We wish to thank Professor Harry B. Gray for his stimulating discussions concerning the spectroscopy of the transition metal hexacarbonyls. This work was supported in part by the U.S. Department of Energy, Contract No. DE-AM03-76F00767; Project Agreement No. DE-AT03-76ER72004. Work performed [by C.F.K.] in partial fulfillment of the requirements for the Ph.D. degree in Chemistry at the California Institute of Technology. Arthur Amos Noyes Laboratory of Chemical Physics, Contribution No. 7131.

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