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A local hybrid exchange functional approximation from first principles

Holzer, Christof 1; Franzke, Yannick J.
1 Institut für Theoretische Festkörperphysik (TFP), Karlsruher Institut für Technologie (KIT)


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 $\textit{ab initio}$ 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 $\textit{g}$-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. ... mehr

Verlagsausgabe §
DOI: 10.5445/IR/1000150417
Veröffentlicht am 22.07.2023
DOI: 10.1063/5.0100439
Zitationen: 13
Web of Science
Zitationen: 12
Zitationen: 15
Cover der Publikation
Zugehörige Institution(en) am KIT Institut für Theoretische Festkörperphysik (TFP)
Publikationstyp Zeitschriftenaufsatz
Publikationsdatum 21.07.2022
Sprache Englisch
Identifikator ISSN: 0021-9606, 1089-7690
KITopen-ID: 1000150417
Erschienen in The Journal of Chemical Physics
Verlag American Institute of Physics (AIP)
Band 157
Heft 3
Seiten Art.Nr. 034108
Nachgewiesen in Dimensions
Web of Science
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