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

Peach, Michael J. G. and Kattirtzi, John A. and Teale, Andrew M. and Tozer, David J. (2010) Shielding Constants and Chemical Shifts in DFT: Influence of Optimized Effective Potential and Coulomb-Attenuation. Journal of Physical Chemistry A, 114 (26). pp. 7179-7186. ISSN 1089-5639

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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.

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Journal Article
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Journal of Physical Chemistry A
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22 Feb 2013 14:16
Last Modified:
21 Sep 2023 01:29