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• W2088600465 endingPage "12136" @default.
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• W2088600465 abstract "We describe the use of Cl K-edge X-ray absorption spectroscopy (XAS) and both ground-state and time-dependent hybrid density functional theory (DFT) to probe the electronic structure and determine the degree of orbital mixing in M-Cl bonds for (C(5)Me(5))(2)MCl(2) (M = Ti, 1; Zr, 2; Hf, 3; Th, 4; U, 5), where we can directly compare a class of structurally similar compounds for d- and f-elements. Pre-edge features in the Cl K-edge XAS data for the group IV transition-metals 1-3 provide direct evidence of covalent M-Cl orbital mixing. The amount of Cl 3p character was experimentally determined to be 25%, 23%, and 22% per M-Cl bond for 1-3, respectively. For actinides, we find a pre-edge shoulder for 4 (Th) and distinct and weak pre-edge features for U, 5. The amount of Cl 3p character was determined to be 9% for 5, and we were unable to make an experimental determination for 4. Using hybrid DFT calculations with relativistic effective core potentials, the electronic structures of 1-5 were calculated and used as a guide to interpret the experimental Cl K-edge XAS data. For transition-metal compounds 1-3, the pre-edge features arise due to transitions from Cl 1s electrons into the 3d-, 4d-, and 5d-orbitals, with assignments provided in the text. For Th, 4, we find that 5f- and 6d-orbitals are nearly degenerate and give rise to a single pre-edge shoulder in the XAS. For U, 5, we find the 5f- and 6d-orbitals fall into two distinct energy groupings, and Cl K-edge XAS data are interpreted in terms of Cl 1s transitions into both 5f- and 6d-orbitals. Time-dependent DFT was used to calculate the energies and intensities of Cl 1s transitions into empty metal-based orbitals containing Cl 3p character and provide simulated Cl K-edge XAS spectra for 1-4. For 5, which has two unpaired 5f electrons, simulated spectra were obtained from transition dipole calculations using ground-state Kohn-Sham orbitals. To the best of our knowledge, this represents the first application of Cl K-edge XAS to actinide systems. Overall, this study allows trends in orbital mixing within a well-characterized structural motif to be identified and compared between transition-metals and actinide elements. These results show that the orbital mixing for the d-block compounds slightly decreases in covalency with increasing principal quantum number, in the order Ti > Zr approximately = Hf, and that uranium displays approximately half the covalent orbital mixing of transition elements." @default.
• W2088600465 created "2016-06-24" @default.
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• W2088600465 date "2009-08-05" @default.
• W2088600465 modified "2023-10-05" @default.
• W2088600465 title "Trends in Covalency for d- and f-Element Metallocene Dichlorides Identified Using Chlorine K-Edge X-ray Absorption Spectroscopy and Time-Dependent Density Functional Theory" @default.
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• W2088600465 doi "https://doi.org/10.1021/ja9015759" @default.
• W2088600465 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/19705913" @default.
• W2088600465 hasPublicationYear "2009" @default.
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