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Spin–Spin Coupling Constant: Overview01:08

Spin–Spin Coupling Constant: Overview

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
Spin–Spin Coupling: One-Bond Coupling01:17

Spin–Spin Coupling: One-Bond Coupling

1.1K
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,...
1.1K
Atomic Nuclei: Nuclear Spin State Overview01:03

Atomic Nuclei: Nuclear Spin State Overview

1.2K
NMR-active nuclei have energy levels called 'spin states' that are associated with the orientations of their nuclear magnetic moments. In the absence of a magnetic field, the nuclear magnetic moments are randomly oriented, and the spin states are degenerate. When an external magnetic field is applied, the spin states have only 2 + 1 orientations available to them. A proton with = ½ has two available orientations. Similarly, for a quadrupolar nucleus with a nuclear spin value of...
1.2K
Spin–Spin Coupling: Two-Bond Coupling (Geminal Coupling)01:20

Spin–Spin Coupling: Two-Bond Coupling (Geminal Coupling)

1.2K
Two NMR-active nuclei bonded to a central atom can be involved in geminal or two-bond coupling. Geminal coupling is commonly seen between diastereotopic protons in chiral molecules and unsymmetrical alkenes, among others.
The central atom need not be NMR-active because its electrons are affected by the electron polarization of the spin-active atoms. However, spin information is transmitted less effectively than in one-bond coupling, and 2J values are usually weaker than 1J values. The energy of...
1.2K
Atomic Nuclei: Nuclear Spin01:08

Atomic Nuclei: Nuclear Spin

3.5K
All atomic particles possess an intrinsic angular momentum, or 'spin'. Electrons, protons, and neutrons each have a spin value of ½, although protons and neutrons in nuclei may have higher half-integer spins owing to energetic factors.
Atomic nuclei have a net nuclear spin, , which can have an integer or half-integer value. In atomic nuclei, the spins of protons are paired against each other but not with neutrons, and vice versa. Consequently, an even number of protons does not...
3.5K
Atomic Nuclei: Nuclear Spin State Population Distribution01:14

Atomic Nuclei: Nuclear Spin State Population Distribution

1.3K
Near absolute zero temperatures, in the presence of a magnetic field, the majority of nuclei prefer the lower energy spin-up state to the higher energy spin-down state. As temperatures increase, the energy from thermal collisions distributes the spins more equally between the two states. The Boltzmann distribution equation gives the ratio of the number of spins predicted in the spin −½ (N−) and spin +½ (N+) states.
1.3K

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Related Experiment Video

Updated: Oct 4, 2025

Spin Saturation Transfer Difference NMR SSTD NMR: A New Tool to Obtain Kinetic Parameters of Chemical Exchange Processes
11:44

Spin Saturation Transfer Difference NMR SSTD NMR: A New Tool to Obtain Kinetic Parameters of Chemical Exchange Processes

Published on: November 12, 2016

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A correctly scaling rigorously spin-adapted and spin-complete open-shell CCSD implementation for arbitrary high-spin

Nils Herrmann1, Michael Hanrath1

  • 1Institute for Theoretical Chemistry, University of Cologne, Greinstraße 4, 50939 Cologne, Germany.

The Journal of Chemical Physics
|February 9, 2022
PubMed
Summary

We developed a novel spin-adapted and spin-complete (SASC) coupled cluster singles and doubles (CCSD) method for high-spin open-shell states. This new implementation offers improved accuracy and convergence for electronic structure calculations.

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Last Updated: Oct 4, 2025

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Area of Science:

  • Quantum Chemistry
  • Computational Chemistry
  • Theoretical Chemistry

Background:

  • Accurate electronic structure calculations are crucial for understanding molecular properties.
  • Coupled Cluster Singles and Doubles (CCSD) is a powerful method but faces challenges with open-shell systems.
  • Existing methods may struggle with spin purity and completeness for high-spin states.

Purpose of the Study:

  • To develop a novel, correctly scaling coupled cluster singles and doubles (CCSD) implementation for arbitrary high-spin open-shell states.
  • To ensure spin completeness and spin adaption (purity) of the coupled cluster wave function.
  • To provide an efficient and accurate computational tool for studying open-shell molecular systems.

Main Methods:

  • Developed a spin-free cluster operator using Löwdin-type operators.
  • Implemented the method using second quantization and factorized tensor contractions.
  • Utilized Wick's theorem and Goldstone diagrams for efficient calculation of spin integration prefactors.
  • Identified and eliminated redundant diagrams via graph isomorphism.
  • Translated non-redundant graphs into factorized tensor contractions.

Main Results:

  • The spin-adapted and spin-complete (SASC) CCSD variant shows reasonable convergence for a Baker-Campbell-Hausdorff series truncation of order four.
  • SASC-CCSD yields slightly improved correlation energies compared to spin orbital CCSD.
  • Demonstrated accuracy with differences up to 1.292 mEH for quintet CH2.

Conclusions:

  • The novel SASC-CCSD implementation is a significant advancement for high-spin open-shell electronic structure calculations.
  • The method ensures spin purity and completeness, leading to more accurate results.
  • This approach offers a promising direction for future computational chemistry studies of open-shell systems.