A Critical Validation of Density Functional and Coupled-Cluster Approaches for the Calculation of EPR Hyperfine Coupling Constants in Transition Metal Complexes

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216224%3A14310%2F99%3A00002120" target="_blank" >RIV/00216224:14310/99:00002120 - isvavai.cz</a>

Výsledek na webu

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DOI - Digital Object Identifier

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Jazyk výsledku

angličtina

Název v původním jazyce

A Critical Validation of Density Functional and Coupled-Cluster Approaches for the Calculation of EPR Hyperfine Coupling Constants in Transition Metal Complexes

Popis výsledku v původním jazyce

The performance of various density functional approaches for the calculation of electron paramagnetic resonance (EPR) hyperfine coupling constants in transition metal complexes has been evaluated critically by comparison with experimental data and high-level coupled-cluster results for 21 systems, representing a large variety of different electronic situations. While both gradient-corrected and hybrid functionals allow the calculation of isotropic metal hyperfine coupling constants to within ca. 10-15%for the less critical cases (e.g., ScO, TiN, TiO, VO, MnO, MnF), none of the functionals investigated performs well for all complexes. Gradient-corrected functionals tend to underestimate the important core-shell spin polarization. While this may be improved by exact-exchange mixing in some cases, the accompanying spin contamination may even lead to a deterioration of the results for other complexes. We also identify cases, where essentially none of the functionals performs satisfactoril

Název v anglickém jazyce

A Critical Validation of Density Functional and Coupled-Cluster Approaches for the Calculation of EPR Hyperfine Coupling Constants in Transition Metal Complexes

Popis výsledku anglicky

The performance of various density functional approaches for the calculation of electron paramagnetic resonance (EPR) hyperfine coupling constants in transition metal complexes has been evaluated critically by comparison with experimental data and high-level coupled-cluster results for 21 systems, representing a large variety of different electronic situations. While both gradient-corrected and hybrid functionals allow the calculation of isotropic metal hyperfine coupling constants to within ca. 10-15%for the less critical cases (e.g., ScO, TiN, TiO, VO, MnO, MnF), none of the functionals investigated performs well for all complexes. Gradient-corrected functionals tend to underestimate the important core-shell spin polarization. While this may be improved by exact-exchange mixing in some cases, the accompanying spin contamination may even lead to a deterioration of the results for other complexes. We also identify cases, where essentially none of the functionals performs satisfactoril

Druh

J_x - Nezařazeno - Článek v odborném periodiku (Jimp, Jsc a Jost)

CEP obor

CF - Fyzikální chemie a teoretická chemie

OECD FORD obor

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Projekt

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Návaznosti

Z - Vyzkumny zamer (s odkazem do CEZ)

Rok uplatnění

1999

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

J. Phys. Chem.

ISSN

A:1089-5639

e-ISSN

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Svazek periodika

103

Číslo periodika v rámci svazku

48

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

17

Strana od-do

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Kód UT WoS článku

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EID výsledku v databázi Scopus

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