Transition metal NMR chemical shifts from optimized effective potentials.
Metal shielding constants and chemical shifts are determined for nine transition metal complexes using an uncoupled formalism with orbitals and eigenvalues determined using the Yang-Wu implementation [W. Yang and Q. Wu, Phys. Rev. Lett. 89, 143002 (2002)] of the optimized effective potential approach in density functional theory. Preliminary calculations using generalized gradient approximation functionals quantify the influence of the variables in the optimized effective potential implementation. In particular, a flexible potential expansion is necessary for a precise calculation of these quantities. Hybrid functionals are then considered. Expanding the potential in the primary orbital basis yields chemical shifts that are a notable improvement over conventional hybrid values, and which are a marginal improvement over those obtained using a high-quality generalized gradient approximation. Similar shifts are obtained using a more flexible potential expansion, although care is required to avoid unphysical structure in the exchange-correlation potential.
Teale
Andrew M
AM
Department of Chemistry, University of Durham, South Road, Durham, DH1 3LE, United Kingdom.
Cohen
Aron J
AJ
Tozer
David J
DJ