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Shielding Constants and Chemical Shifts in DFT: Influence of Optimized Effective Potential and Coulomb-Attenuation

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<mark>Journal publication date</mark>8/07/2010
<mark>Journal</mark>Journal of Physical Chemistry A
Issue number26
Number of pages8
Pages (from-to)7179-7186
Publication StatusPublished
<mark>Original language</mark>English


The influence of the optimized effective potential (OEP) and Coulomb-attenuation on shielding constants and chemical shifts is investigated for three disparate categories of molecule: main group, hydrogen bonded, and transition metal systems. Expanding the OEP in the orbital basis leads to physically sensible exchange-correlation potentials; OEP generalized gradient approximation results provide some indication of the accuracy of the expansion. OEP uncoupled magnetic parameters from representative hybrid and Coulomb-attenuated functionals can be a dramatic improvement over conventional results; both categories yield similar accuracy. Additional flexibility is introduced by expanding the OEP in an extensive even-tempered basis set, but this leads to the well-known problem of unphysical, oscillatory potentials. Smooth potentials are recovered through the use of a smoothing norm, but deficiencies in the procedure are highlighted for transition metal complexes. The study reiterates the importance of the OEP procedure in magnetic response calculations using orbital-dependent functionals, together with the need for careful attention to ensure physically sensible potentials. It also illustrates the utility of Coulomb-attenuated functionals for computing short-range molecular properties.