Spin-Symmetry Breaking and Hyperfine Couplings in Transition-Metal Complexes Revisited Using Density Functionals Based on the Exact-Exchange Energy Density

Overview

Journal J Chem Theory Comput

Publisher American Chemical Society

Specialties Biochemistry
Chemistry

Date 2024 Feb 27

PMID 38411554

Authors

Artur Wodynski

Bryan Lauw

Marc Reimann

Martin Kaupp

Affiliations

Soon will be listed here.

Abstract

A small set of mononuclear manganese complexes evaluated previously for their Mn hyperfine couplings (HFCs) has been analyzed using density functionals based on the exact-exchange energy density─in particular, the spin symmetry breaking (SSB) found previously when using hybrid functionals. Employing various strong-correlation corrected local hybrids (scLHs) and strong-correlation corrected range-separated local hybrids (scRSLHs) with or without additional corrections to their local mixing functions (LMFs) to mitigate delocalization errors (DE), the SSB and the associated dipolar HFCs of [Mn(CN)], MnO, [Mn(CN)N], and [Mn(CN)NO] (the latter with cluster embedding) have been examined. Both strong-correlation (sc)-correction and DE-correction terms help to diminish SSB and correct the dipolar HFCs. The DE corrections are more effective, and the effects of the sc corrections depend on their damping factors. Interestingly, the DE-corrections reduce valence-shell spin polarization (VSSP) and thus SSB by locally enhancing exact-exchange (EXX) admixture near the metal center and thereby diminishing spin-density delocalization onto the ligand atoms. In contrast, sc corrections diminish EXX admixture locally, mostly on specific ligand atoms. This then reduces VSSP and SSB as well. The performance of scLHs and scRSLHs for the isotropic Mn HFCs has also been analyzed, with particular attention to core-shell spin-polarization contributions. Further sc-corrected functionals, such as the KP16/B13 construction and the DM21 deep-neural-network functional, have been examined.

Citing Articles

Toward the Next Generation of Density Functionals: Escaping the Zero-Sum Game by Using the Exact-Exchange Energy Density.

Kaupp M, Wodynski A, Arbuznikov A, Furst S, Schattenberg C Acc Chem Res. 2024; 57(13):1815-1826.

PMID: 38905497 PMC: 11223257. DOI: 10.1021/acs.accounts.4c00209.

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