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• W2599194239 endingPage "25" @default.
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• W2599194239 abstract "Abstract In this work, a general, user-friendly method – ab initio ligand field theory (AILFT), is described and illustrated. AILFT allows one to unambiguously extract all ligand field parameters (the ligand field one-electron matrix V LFT , the Racah parameters B and C , and the spin-orbit coupling parameter ζ ) from relatively straightforward multi-reference ab initio calculations. The method applies to mononuclear complexes in d n or f n configurations. The method is illustrated using complete active space self-consistent field (CASSCF) and N-electron valence perturbation theory (NEVPT2) calculations on a series of well documented octahedral complexes of Cr III with simple ligands such as F − , Cl − , Br − , I − , NH 3 and CN − . It is shown that all well-known trends for the value of 10 Dq (the spectrochemical series) are faithfully reproduced by AILFT. By comparison of B and ζ for Cr III in these complexes with the parameters calculated for the free ion Cr 3+ , the covalency of the Cr-ligand bond can be assessed quantitatively (the non-relativistic and relativistic nephelauxetic effects). The variation of ligand field parameters for complexes of 3d, 4d and 5d elements is studied using MCl 6 3− (M = Cr III , Mo III , W III ) as model examples. As reflected in variations of 10 Dq , B and ζ across this series, metal-ligand covalency increases from CrCl 6 3− to MoCl 6 3− to WCl 6 3− . Using the angular overlap model, the one-electron parameters of the ligand field matrix are decomposed into increments for σ- and π- metal-ligand interactions. This allows for the quantification of variations in σ- and π-ligand donor properties of these ligands. Using these results, the well documented two-dimensional spectroscopic series for complexes of Cr III is quantitatively reproduced. Comparison of the results obtained using CASSCF and NEVPT2 reveals the importance of dynamic electron correlation. Finally, the limitations of the AILFT method for complexes with increasing metal-ligand covalency are analyzed and discussed." @default.
• W2599194239 created "2017-04-07" @default.
• W2599194239 creator A5030106158 @default.
• W2599194239 creator A5038787666 @default.
• W2599194239 creator A5046820685 @default.
• W2599194239 creator A5084689584 @default.
• W2599194239 date "2017-08-01" @default.
• W2599194239 modified "2023-10-13" @default.
• W2599194239 title "Covalency and chemical bonding in transition metal complexes: An ab initio based ligand field perspective" @default.
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