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Related Concept Videos

Symmetry Elements in a Crystal01:27

Symmetry Elements in a Crystal

Crystal symmetry operations are isometric transformations that map objects onto indistinguishable copies while preserving distances, angles, and volumes. The simplest symmetry operation is translation, which shifts the entire infinite crystal lattice parallelly by a translation vector.Crystallographic rotations involve rotations by an angle of 2π/n around an axis without changing the positions of points on the axis. It is called the rotational axis of the symmetry, denoted by n. The combination...
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...
Woodward–Hoffmann Selection Rules and Microscopic Reversibility01:34

Woodward–Hoffmann Selection Rules and Microscopic Reversibility

Electrocyclic reactions, cycloadditions, and sigmatropic rearrangements are concerted pericyclic reactions that proceed via a cyclic transition state. These reactions are stereospecific and regioselective. The stereochemistry of the products depends on the symmetry characteristics of the interacting orbitals and the reaction conditions. Accordingly, pericyclic reactions are classified as either symmetry-allowed or symmetry-forbidden. Woodward and Hoffmann presented the selection criteria for...
Valence Bond Theory02:42

Valence Bond Theory

Coordination compounds and complexes exhibit different colors, geometries, and magnetic behavior, depending on the metal atom/ion and ligands from which they are composed. In an attempt to explain the bonding and structure of coordination complexes, Linus Pauling proposed the valence bond theory, or VBT, using the concepts of hybridization and the overlapping of the atomic orbitals. According to VBT, the central metal atom or ion (Lewis acid) hybridizes to provide empty orbitals of suitable...
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: Three-Bond Coupling (Vicinal Coupling)01:22

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

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 involved orbitals. The...

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Internal symmetry of basic elements in symmetry-based recoupling sequences under magic-angle spinning.

Fang-Chieh Chou1, Hsin-Kuan Lee, Jerry C C Chan

  • 1Department of Chemistry, National Taiwan University, No. 1, Section 4, Roosevelt Road, Taipei 106, Taiwan.

The Journal of Chemical Physics
|September 28, 2010
PubMed
Summary

Researchers discovered internal selection rules in symmetry-based recoupling pulse sequences for solid-state NMR. These rules enable versatile design of advanced pulse sequences, like C-REDOR, for improved heteronuclear dipolar recoupling.

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Published on: June 7, 2018

Area of Science:

  • Solid-state Nuclear Magnetic Resonance (NMR) spectroscopy.
  • Quantum information processing and control.
  • Materials science and structural analysis.

Background:

  • Symmetry-based pulse sequences are crucial for solid-state NMR under magic-angle spinning.
  • Existing C- and R-sequences provide a framework for analyzing these powerful techniques.
  • The internal symmetries of basic elements within these sequences have been hypothesized but not fully elucidated.

Purpose of the Study:

  • To investigate and demonstrate the existence of internal selection rules in basic elements of symmetry-based recoupling pulse sequences.
  • To explore how these rules can facilitate the design of novel NMR pulse sequences.
  • To validate the derived symmetry arguments through experimental and simulation data.

Main Methods:

  • Detailed theoretical analysis of symmetry properties within basic recoupling elements.
  • Derivation of internal selection rules governing sequence behavior.
  • Application of symmetry arguments to rationalize existing sequences like C-REDOR.
  • Design of new windowed elements for heteronuclear dipolar recoupling with homonuclear suppression.
  • Validation using numerical simulations and experimental solid-state NMR on [U-(13)C,(15)N]-L-alanine.

Main Results:

  • Confirmed the existence of internal selection rules for many basic elements in symmetry-based recoupling sequences.
  • Demonstrated that these rules enable more versatile design of CN(n)(ν) and RN(n)(ν) sequences.
  • Rationalized the homonuclear dipole-dipole interaction suppression in C-REDOR.
  • Successfully designed new windowed elements for selective heteronuclear dipolar recoupling.
  • Validated the theoretical framework through simulations and experimental data.

Conclusions:

  • The identified internal selection rules offer a powerful tool for designing advanced solid-state NMR pulse sequences.
  • These rules facilitate the development of sequences with specific recoupling properties and suppression capabilities.
  • The principles discussed are broadly applicable, including the design of supercycles and optimization of spectral resolution.