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Coupling interactions are strongest between NMR-active nuclei bonded to each other, where spin information can be transmitted directly through the pair of bonding electrons. While nuclei polarize their electrons to the opposite spins, the bonding electron pair has opposite spins. Configurations with antiparallel nuclear spins are expected to be lower in energy. When coupling makes antiparallel states more favorable, J is considered to have a positive value. The one-bond coupling constant, 1J,...
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Spin systems where the difference in chemical shifts of the coupled nuclei is greater than ten times J are called first-order spin systems. These nuclei are weakly coupled, and their chemical shifts and coupling constant can generally be estimated from the well-separated signals in the spectrum.
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Vicinal or three-bond coupling is commonly observed between protons attached to adjacent carbons. Here, nuclear spin information is primarily transferred via electron spin interactions between adjacent C‑H bond orbitals. This generally favors the antiparallel arrangement of spins, so 3J values are usually positive.
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Benchmarking isotropic hyperfine coupling constants using (QTP) DFT functionals and coupled cluster theory.

Zachary W Windom1, Ajith Perera1, Rodney J Bartlett1

  • 1Quantum Theory Project, University of Florida, Gainesville, Florida 32611-8435, USA.

The Journal of Chemical Physics
|March 9, 2022
PubMed
Summary
This summary is machine-generated.

We benchmarked 24 Density Functional Theory (DFT) functionals for predicting isotropic hyperfine coupling constants in radicals. CAM-QTP01 and CAM-QTP02 show high accuracy, especially for transition metal complexes, while hybrid DFT functionals offer a good balance.

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Area of Science:

  • Computational Chemistry
  • Quantum Chemistry
  • Theoretical Chemistry

Background:

  • Accurate prediction of isotropic hyperfine coupling constants is crucial for fitting experimental model Hamiltonians.
  • Previous studies have focused on wavefunction and Density Functional Theory (DFT) approaches, but few have examined DFT functionals satisfying the Bartlett ionization potential (IP) condition.
  • There is a need to evaluate DFT functionals for their predictive power on hyperfine coupling constants across various radical types.

Purpose of the Study:

  • To benchmark the performance of 24 commonly used DFT functionals for predicting isotropic hyperfine coupling constants.
  • To specifically assess the Quantum Theory Project (QTP) functionals (CAM-QTP00, CAM-QTP01, CAM-QTP02, QTP17) for this property.
  • To compare DFT predictions with coupled-cluster singles and doubles (CCSD) and CCSD(T) results for organic radicals.

Main Methods:

  • Prediction of isotropic hyperfine coupling constants for 56 radicals using 24 DFT functionals.
  • Inclusion of small and large organic radicals, as well as transition metal complexes.
  • Validation using coupled-cluster singles and doubles (CCSD) and CCSD with perturbative triples [CCSD(T)] calculations for select organic radicals.

Main Results:

  • The QTP17 and CAM-QTP00 functionals underperformed, despite being parameterized for an IP eigenvalue condition.
  • The CAM-QTP01 functional demonstrated the highest accuracy for both organic radical datasets.
  • CAM-QTP01 and CAM-QTP02 were the most accurate functionals for the transition metal complex dataset.
  • Hybrid DFT functionals generally provided an optimal balance between accuracy and precision across all datasets.

Conclusions:

  • CAM-QTP01 emerges as a highly accurate functional for predicting isotropic hyperfine coupling constants in organic radicals.
  • CAM-QTP01 and CAM-QTP02 are recommended for studies involving transition metal complexes.
  • Hybrid DFT functionals offer a reliable choice for general applications requiring a balance of accuracy and computational efficiency.