title: Transition metal NMR chemical shifts from optimized effective potentials.
abstract: 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.
authors.affiliation: Department of Chemistry, University of Durham, South Road, Durham, DH1 3LE, United Kingdom.
authors.forename: Andrew M
authors.initials: AM
authors.lastname: Teale
authors.forename: Aron J
authors.initials: AJ
authors.lastname: Cohen
authors.forename: David J
authors.initials: DJ
authors.lastname: Tozer