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Spin–Spin Coupling: One-Bond Coupling01:17

Spin–Spin Coupling: One-Bond Coupling

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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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¹H NMR: Interpreting Distorted and Overlapping Signals01:02

¹H NMR: Interpreting Distorted and Overlapping Signals

1.1K
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.
As Δν decreases and the signals move closer, the doublets appear increasingly distorted. The intensities of the inner lines increase at the cost of those of the outer lines as the signals are...
1.1K
Spin–Spin Coupling: Three-Bond Coupling (Vicinal Coupling)01:22

Spin–Spin Coupling: Three-Bond Coupling (Vicinal Coupling)

1.2K
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.
The extent of coupling depends on the C‑C bond length, the two H‑C‑C angles, any electron-withdrawing substituents, and the dihedral angle between the...
1.2K
Spin–Spin Coupling Constant: Overview01:08

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1.0K
In bromoethane, the three methyl protons are coupled to the two methylene protons that are three bonds away. In accordance with the n+1 rule, the signal from the methyl protons is split into three peaks with 1:2:1 relative intensities. The methylene protons appear as a quartet, with the relative intensities of 1:3:3:1.
Qualitatively, any spin plus-half nucleus polarizes the spins of its electrons to the minus-half state. Consequently, the paired electron in the hydrogen–carbon bond must...
1.0K
Hybridization of Atomic Orbitals II03:35

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sp3d and sp3d 2 Hybridization
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¹H NMR: Long-Range Coupling01:27

¹H NMR: Long-Range Coupling

2.0K
The coupling interactions of nuclei across four or more bonds are usually weak, with J values less than 1 Hz. While these are usually not observed in spectra, the presence of multiple bonds along the coupling pathway can result in observable long-range coupling.
In alkenes, spin information is communicated via σ–π overlap, as seen in allylic (four-bond) and homoallylic (five-bond) couplings. These coupling interactions are stronger when the σ bond is parallel to the alkene...
2.0K

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Related Experiment Video

Updated: Oct 1, 2025

Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry
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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.