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Spin–Spin Coupling Constant: Overview01:08

Spin–Spin Coupling Constant: Overview

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 have a...
Spin–Spin Coupling: One-Bond Coupling01:17

Spin–Spin Coupling: One-Bond Coupling

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,...
Spin–Spin Coupling: Two-Bond Coupling (Geminal Coupling)01:20

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

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...
Correlation of Experimental Data01:23

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Dimensional analysis simplifies complex physical problems and guides experimental investigations, but it does not provide complete solutions. It identifies the dimensionless groups that influence a phenomenon, but experimental data is needed to establish the specific relationships and validate theoretical predictions.
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Related Experiment Video

Updated: Jul 4, 2026

In Situ Monitoring of Diffusion of Guest Molecules in Porous Media Using Electron Paramagnetic Resonance Imaging
06:34

In Situ Monitoring of Diffusion of Guest Molecules in Porous Media Using Electron Paramagnetic Resonance Imaging

Published on: September 2, 2016

The direct DIVAM experiment: a spin dynamics analysis.

Paul Hazendonk1, Philip Wormald, Tony Montina

  • 1Department of Chemistry and Biochemistry, University of Lethbridge, Lethbridge, Alberta T1K 3M4, Canada. paul.hazendonk@uleth.ca

The Journal of Physical Chemistry. A
|June 24, 2008
PubMed
Summary

The DIVAM experiment in polymer NMR allows selective signal detection from specific domains. By tuning parameters, it can act as a relaxation filter or leverage coherent interactions like chemical shift anisotropy for domain selection.

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Last Updated: Jul 4, 2026

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Area of Science:

  • Nuclear Magnetic Resonance (NMR) Spectroscopy
  • Polymer Science
  • Physical Chemistry

Background:

  • Polymer NMR domain selection is typically limited to specific experiments for each domain's unique properties.
  • Existing methods struggle to isolate signals from different domains within a single experiment.
  • The DIVAM sequence offers tunable domain selection, but its underlying mechanisms require further exploration.

Purpose of the Study:

  • To investigate the role of coherent terms in the direct DIVAM (DD) experiment for polymer NMR domain selection.
  • To explore how parameters like chemical shift anisotropy (CSA) and offset frequency influence DD sequence performance.
  • To develop an analytical model for DD signal intensity considering relaxation and coherent evolution.

Main Methods:

  • Utilized SIMPSON simulations to model the behavior of the DD sequence.
  • Analyzed experimental data showing transient signal intensity behavior on the sample spinning time scale.
  • Derived an analytical expression for signal intensity using a one-spin-relaxation model incorporating chemical shift evolution.

Main Results:

  • Coherent terms, particularly CSA and offset frequency, significantly influence domain selection in the DD sequence.
  • Dipolar coupling was found to be less effective for domain selection compared to CSA and offset terms.
  • The DD sequence's behavior transitions from a relaxation filter to a coherent interaction filter based on excitation angle and delay times.
  • An analytical model confirmed the dependence of signal intensity on interpulse delay, excitation angle, relaxation time, and offset frequency.

Conclusions:

  • The direct DIVAM (DD) sequence provides versatile domain selection in polymer NMR by tuning the excitation angle.
  • DD can be optimized to function as either a relaxation rate filter or a chemical shift anisotropy (CSA) interaction filter.
  • Understanding the interplay of coherent and incoherent processes is crucial for effective domain-specific NMR signal extraction.