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

The result's identifiers

  • Result code in 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>

  • Result on the web

  • DOI - Digital Object Identifier

Alternative languages

  • Result language

    angličtina

  • Original language name

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

  • Original language description

    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

  • Czech name

  • Czech description

Classification

  • Type

    J<sub>x</sub> - Unclassified - Peer-reviewed scientific article (Jimp, Jsc and Jost)

  • CEP classification

    CF - Physical chemistry and theoretical chemistry

  • OECD FORD branch

Result continuities

  • Project

  • Continuities

    Z - Vyzkumny zamer (s odkazem do CEZ)

Others

  • Publication year

    1999

  • Confidentiality

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

Data specific for result type

  • Name of the periodical

    J. Phys. Chem.

  • ISSN

    A:1089-5639

  • e-ISSN

  • Volume of the periodical

    103

  • Issue of the periodical within the volume

    48

  • Country of publishing house

    US - UNITED STATES

  • Number of pages

    17

  • Pages from-to

  • UT code for WoS article

  • EID of the result in the Scopus database