An Evaluation of Modern Density Functionals for the Bond Dissociation Energies of Diatomic Transition Metal Complexes.
Abstract
Two benchmark sets of dissociation energies of diatomic transition-metal complexes have been assembled from previously published data, with selected reference values reassessed or updated where necessary, and used to evaluate a variety of density functionals. The BDE41 set of 41 3d complexes based on both experimental data and phaseless auxiliary-field quantum Monte Carlo reference data is the statistically more robust of the two sets. A number of local hybrid functionals top the list with the smallest deviations, including the strong-correlation (sc) corrected scLH22t and scLH22ta, and the range-separated variant ωLH23tP, followed by the previous top-performing global hybrids B97 and B97-1. While global hybrids and local hybrids without sc-corrections tend to underbind on average, sc-corrections may shift this to moderate overbinding. Nitride and oxide complexes account for much of the underbinding. Functionals based on neural-network local mixing functions underbind more clearly also in other cases, confirming that for these very flexible constructions a lack of transition-metal training data is more harmful to transferability than for less flexible functionals with heuristic mixing functions. The smaller and somewhat less reliable HBDE17 set of 4d/5d complexes reinforces several of the observations but appears to disfavor large exact-exchange admixtures even more strongly. In this case carbide and oxide complexes provide the most pronounced challenges. Nevertheless, several functionals perform not much worse than the most sophisticated post-Hartree-Fock reference calculations currently available based on CCSD(T) with multi-reference corrections. These benchmark sets may also prove useful for training and evaluating new approximate methods, an application we intend to explore in future work.
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BibTeX
@misc{weber2026evaluation,
title = {{An Evaluation of Modern Density Functionals for the Bond Dissociation Energies of Diatomic Transition Metal Complexes.}},
author = {Adrian Rodriguez Weber and Nóra Kovács and Artur Wodyński and Martin Kaupp},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.15011045/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15011045/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - An Evaluation of Modern Density Functionals for the Bond Dissociation Energies of Diatomic Transition Metal Complexes.
AU - Adrian Rodriguez Weber
AU - Nóra Kovács
AU - Artur Wodyński
AU - Martin Kaupp
PY - 2026
DA - 2026/10/26
PB - ChemRxiv
DO - 10.26434/chemrxiv.15011045/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15011045/v1
AB - Two benchmark sets of dissociation energies of diatomic transition-metal complexes have been assembled from previously published data, with selected reference values reassessed or updated where necessary, and used to evaluate a variety of density functionals. The BDE41 set of 41 3d complexes based on both experimental data and phaseless auxiliary-field quantum Monte Carlo reference data is the statistically more robust of the two sets. A number of local hybrid functionals top the list with the smallest deviations, including the strong-correlation (sc) corrected scLH22t and scLH22ta, and the range-separated variant ωLH23tP, followed by the previous top-performing global hybrids B97 and B97-1. While global hybrids and local hybrids without sc-corrections tend to underbind on average, sc-corrections may shift this to moderate overbinding. Nitride and oxide complexes account for much of the underbinding. Functionals based on neural-network local mixing functions underbind more clearly also in other cases, confirming that for these very flexible constructions a lack of transition-metal training data is more harmful to transferability than for less flexible functionals with heuristic mixing functions. The smaller and somewhat less reliable HBDE17 set of 4d/5d complexes reinforces several of the observations but appears to disfavor large exact-exchange admixtures even more strongly. In this case carbide and oxide complexes provide the most pronounced challenges. Nevertheless, several functionals perform not much worse than the most sophisticated post-Hartree-Fock reference calculations currently available based on CCSD(T) with multi-reference corrections. These benchmark sets may also prove useful for training and evaluating new approximate methods, an application we intend to explore in future work.
ER -