A Look at Real‐World Transition‐Metal Thermochemistry and Kinetics with Local Hybrid Functionals
Abstract: Local hybrid functionals (LHs) use a position‐dependent admixture of exact exchange in real space, which has previously been shown to offer various advantages over global hybrids and the potential to construct functionals with wide applicability. While main‐group thermochemistry and kinetics and other properties have already been studied extensively, no broad and systematic investigation for the energetics of transition‐metal complexes has been reported so far for LHs. To close this gap, we evaluate eight LHs for three previously reported test sets on barrier heights and reaction energies of real‐world transition metal complexes, in comparison with several other rung‐4 hybrid functionals. The recent LH20t‐D4 method emerges as the top‐performing functional for the overall benchmark, comparable to the simpler TPSS0‐D4 and slightly before the more complex range‐separated ωB97M‐V. But LH20t‐D4 and ωB97M‐V perform much better for main‐group energetics, making them overall more reliable tools to study organometallic reaction mechanisms. Given also its previously observed excellent performance for mixed‐valence systems, LH20t‐D4 is thus a widely applicable functional in both main‐group and transition‐metal chemistry, while also providing convincing accuracy for many spectroscopic properties. The earlier LH14t‐calPBE‐D4 local hybrid also performs well, while some first‐generation LHs fall behind.
- Location
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Deutsche Nationalbibliothek Frankfurt am Main
- Extent
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Online-Ressource
- Language
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Englisch
- Bibliographic citation
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A Look at Real‐World Transition‐Metal Thermochemistry and Kinetics with Local Hybrid Functionals ; day:06 ; month:07 ; year:2022 ; extent:1
Israel journal of chemistry ; (06.07.2022) (gesamt 1)
- Creator
- DOI
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10.1002/ijch.202200021
- URN
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urn:nbn:de:101:1-2022070615183404297203
- Rights
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Open Access; Der Zugriff auf das Objekt ist unbeschränkt möglich.
- Last update
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15.08.2025, 7:23 AM CEST
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Deutsche Nationalbibliothek. If you have any questions about the object, please contact the data provider.
Associated
- Grotjahn, Robin
- Kaupp, Martin
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Assessment and contributions to local hybrid functionals
Implementation and first evaluation of strong-correlation-corrected local hybrid functionals for the calculation of NMR shieldings and shifts
Spin-symmetry breaking and hyperfine couplings in transition-metal complexes revisited using density functionals based on the exact-exchange energy density
Implementation of modern density functional methods : gradients for local hybrid functionals and SCF for local range-separated hybrid functionals
Quantum chemical studies of transition-metal complexes and aqueous solvent effects
Development of local hybrid functionals for time-dependent density functional theory
Toward a correct treatment of core properties with local hybrid functionals
Development, implementation and validation of excited-state gradients for local hybrid functionals
Quantum-chemical studies of inorganic electronic structure and reactivity : from unusual silicon and germanium compounds to transition-metal catalysis
A Look at Real‐World Transition‐Metal Thermochemistry and Kinetics with Local Hybrid Functionals
Kaupp, Martin
Kaupp, Martin
Assessment and contributions to local hybrid functionals
Implementation and first evaluation of strong-correlation-corrected local hybrid functionals for the calculation of NMR shieldings and shifts
Spin-symmetry breaking and hyperfine couplings in transition-metal complexes revisited using density functionals based on the exact-exchange energy density
Implementation of modern density functional methods : gradients for local hybrid functionals and SCF for local range-separated hybrid functionals
Quantum chemical studies of transition-metal complexes and aqueous solvent effects
Development of local hybrid functionals for time-dependent density functional theory
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