The multi-configurational short-range (sr) density functional theory has been extended to the calculation of indirect spin–spin coupling constants (SSCCs) for nuclear magnetic resonance spectroscopy. The performance of the new method is compared to Kohn–Sham density functional theory and the ab initio complete active space self-consistent field for a selected set of molecules with good reference values. Two density functionals have been considered, the local density approximation srLDA and srPBE from the GGA class of functionals. All srDFT calculations are of Hartree–Fock-type HF-srDFT or complete active space-type CAS-srDFT. In all cases, the calculated SSCC values are of the same quality for srLDA and srPBE functionals, suggesting that one should use the computationally cost-effective srLDA functionals in applications. For all the calculated SSCCs in organic compounds, the best choice is HF-srDFT; the more expensive CAS-srDFT does not provide better values for these single-reference molecules. Fluorine is a challenge; in particular, the FF, FC, and FO couplings have much higher statistical errors than the rest. For SSCCs involving fluorine and a metal atom CAS-srDFT with singlet, generalized Tamm–Dancoff approximation is needed to get good SSCC values although the reference ground state is not a multi-reference case. For , all other considered models fail blatantly.
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28 August 2021
Research Article|
August 26 2021
Multi-configurational short-range density functional theory can describe spin–spin coupling constants of transition metal complexes
Erik Rosendahl Kjellgren
;
Erik Rosendahl Kjellgren
Department of Physics, Chemistry and Pharmacy, University of Southern Denmark
, DK-5230 Odense M, Denmark
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Hans Jørgen Aagaard Jensen
Hans Jørgen Aagaard Jensen
a)
Department of Physics, Chemistry and Pharmacy, University of Southern Denmark
, DK-5230 Odense M, Denmark
a)Author to whom correspondence should be addressed: hjj@sdu.dk
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a)Author to whom correspondence should be addressed: hjj@sdu.dk
J. Chem. Phys. 155, 084102 (2021)
Article history
Received:
June 06 2021
Accepted:
August 07 2021
Citation
Erik Rosendahl Kjellgren, Hans Jørgen Aagaard Jensen; Multi-configurational short-range density functional theory can describe spin–spin coupling constants of transition metal complexes. J. Chem. Phys. 28 August 2021; 155 (8): 084102. https://doi.org/10.1063/5.0059128
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