The calculation of 17O chemical shielding in transition metal oxo complexes. I. Comparison of DFT and ab initio approaches, and mechanisms of relativity-induced shielding

The performance of different DFT (UDFT-IGLO, UDFT-GIAO, SOS-DFPT-IGLO) and hybrid-DFT approaches, as well as of HF-GIAO and MP2-GIAO methods has been compared for the calculation of 17O chemical shielding in the series of tetrahedral d0 oxo complexes MO4(M=Fe,Ru,Os), MO4−(M=Mn,Tc,Re), and MO42−(M=Cr,Mo,W). While HF-GIAO and MP2-GIAO fail for systems with low-lying excited states (e.g., MnO4−, CrO42−, or MO4), the DFT methods consistently remain remarkably stable. Larger basis sets change the results little, SOS-DFPT correction terms are small, and differences between different local and gradient-corrected exchange-correlation functionals are also minor. The inclusion of CHF-type coupling terms for DFT-HF hybrid functionals leads to a significant overestimate of the paramagnetic contributions, the neglect of these terms to an equally large underestimate. DFT-IGLO results for the 3d complexes show an unexpectedly large dependence on whether the metal semicore shells are localized separately or together with...

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