A Local Hybrid Exchange Functional Approximation from First Principles

Local hybrid functionals are a more flexible class of density functional approximations allowing for a position-dependent admixture of exact exchange. This additional flexibility, however, comes with a more involved mathematical form and a more complicated design. A common denominator for previously constructed local hybrid funtionals is usage of thermochemical benchmark data to construct these functionals. Herein, we design a local hybrid functional without relying on benchmark data. Instead, we construct it in a more ab initio manner, following the principles of modern meta-generalized gradient approximations and considering theoretical constrains. To achieve this, we make use of the density matrix expansion and a local mixing function based on an approximate correlation length. The accuracy of the developed density functional approximation is assessed for thermochemistry, excitation energies, polarizabilities, magnetizabilities, NMR spin–spin coupling constants, NMR shieldings and shifts, as well as EPR g-tensors and hyperfine coupling constants. Here, the new exchange functional shows a robust performance and is especially well suited for atomization energies, barrier heights, excitation energies, NMR coupling constants, and EPR properties, whereas it looses some ground for the NMR shifts. Therefore, the designed functional is a major step forwards for functionals that have been designed from first principles.