A local hybrid exchange functional approximation from first principles
Year: 2022
Type: article
Abstract: 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 functionals is the 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 constraints. 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, nuclear magnetic resonance (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 loses some ground for the NMR shifts. Therefore, the designed functional is a major step forward for functionals that have been designed from first principles.
Source: The Journal of Chemical Physics
DOI: 10.1063/5.0100439
Authors: Christof Holzer, Yannick J. Franzke
Language: English
Subfield: Atomic and Molecular Physics, and Optics
Field: Physics and Astronomy
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $3,500
Funders: TURBOMOLE, Volkswagen Foundation
OpenAlex ID: W4283688451