Inner-shell excitation of 3d transition-metal carbonyls (Mn sub 2 (CO) sub 10 , Mn(CO) sub 5 Br, and Mn(CO) sub 5 H) studied by electron energy loss spectroscopy
- McMaster Univ., Hamilton, Ontario (Canada)
The C 1s and O 1s spectra of Mn{sub 2}(CO){sub 10}, Mn(CO){sub 5}Br, and Mn(CO){sub 5}H, along with the Mn 3p and Mn 2p spectra of Mn{sub 2}(CO){sub 10} and Mn(CO){sub 5}Br, have been recorded with inelastic electron scattering under conditions dominated by electric dipole transitions. The C 1s and O 1s spectra, converted to absolute oscillator strength scales, are analyzed in comparison to those of free CO and of other metal carbonyls. The oscillator strengths of the carbon and oxygen 1s {yields} {pi}* transitions are found to shift systematically with changes in the ligand and the transition metal, in a fashion consistent with the relative extent of d{pi} - p{pi} back-bonding. In contrast, the relationship between 1s {yields} {pi}* energies or term values and ground-state d{pi}-p{pi} back-bonding is less direct because of differences in the relaxation (core hole polarization) of the core-excited and core-ionized states. The relationship between 1s {yields} {sigma}* energies and C-O bond lengths is considered. It is found that the main line in photoemission does not provide a suitable reference for correlations between 1s {yields} {sigma}* energies and C-O bond lengths. Alternate choices for reference energies are discussed.
- OSTI ID:
- 5208138
- Journal Information:
- Journal of the American Chemical Society; (USA), Vol. 111:7, Issue 7; ISSN 0002-7863
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
BROMIDES
ELECTRONIC STRUCTURE
CARBONYLS
HYDRIDES
MANGANESE COMPLEXES
CATALYSTS
ENERGY-LOSS SPECTROSCOPY
EXPERIMENTAL DATA
OSCILLATOR STRENGTHS
PHOTOCHEMICAL REACTIONS
BROMINE COMPOUNDS
CHEMICAL REACTIONS
COMPLEXES
DATA
ELECTRON SPECTROSCOPY
HALIDES
HALOGEN COMPOUNDS
HYDROGEN COMPOUNDS
INFORMATION
NUMERICAL DATA
SPECTROSCOPY
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties
400500 - Photochemistry