Assessing the Accuracy of Local Hybrid Density Functional Approximations for Molecular Response Properties
Christof Holzer, Yannick J. Franzke, Max Kehry
Abstract
A comprehensive overview of the performance of local hybrid functionals for molecular properties like excited states, ionization potentials within the GW framework, polarizabilities, magnetizabilities, NMR chemical shifts, and NMR spin–spin coupling constants is presented. We apply the generalization of the kinetic energy, τ, with the paramagnetic current density to all magnetic properties and the excitation energies from time-dependent density functional theory. This restores gauge invariance for these properties. Different ansätze for local mixing functions such as the iso-orbital indicator, the correlation length, the Görling–Levy second-order limit, and the spin polarization are compared. For the latter, we propose a modified version of the corresponding hyper-generalized gradient approximation functional of Perdew, Staroverov, Tao, and Scuseria (PSTS) [Phys. Rev. A 2008, 78, 052513] to allow for a numerically stable evaluation of the exchange-correlation kernel and hyperkernel. The PSTS functional leads to a very consistent improvement compared to the related TPSSh functional. It is further shown that the “best” choice of the local mixing function depends on the studied property and molecular class. While functionals based on the iso-orbital indicator lead to rather accurate excitation energies and ionization energies, the results are less impressive for NMR properties, for which a considerable dependence on the considered molecular test set and nuclei is observed. Johnson’s local hybrid functional based on the correlation length yields remarkable results for NMR shifts of compounds featuring heavy elements and also for the excitation energies of organic compounds.