Journal
INORGANIC CHEMISTRY
Volume 50, Issue 14, Pages 6767-6774Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ic200822b
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- Cornell University
- ACS [50270-DN13]
- National Science Foundation
- National Institutes of Health/National Institute of General Medical Sciences under NSF [DMR-0936384]
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K beta X-ray emission spectroscopy (XES) is emerging as a powerful tool for the study of chemical bonding. Analyses of the K beta XES of ferrocene (Fc) and ferrocenium (Fc(+)) are presented as further demonstrations of the capabilities of the technique. Assignments of the valence to core (V2C) region of these spectra as electric dipole-allowed cyclopentadienyl (Cp) -> Fe Is transitions demonstrate that XES affords electronic structural insight into the energetics of ligand-based molecular orbitals (MOs). Combined with K-edge X-ray absorption spectroscopy (XAS), we show that XES can provide analogous information to photoemission spectroscopy (PES). Density functional theory (DFT) analyses reveal that the V2C transitions in Fc/Fc(+) derive their intensity from Fe 4p admixture (on the order of 5-10%) into the Cp-based MOs from which they originate. These 4p admixtures confer bonding character to the Cp-based a(2u) and e(1u), MOs to at least the extent of backbonding contributions to frontier MOs from higher-lying Cp pi* MOs.
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