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NMR Spectroscopy: Spin–Spin Coupling01:08

NMR Spectroscopy: Spin–Spin Coupling

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The spin state of an NMR-active nucleus can have a slight effect on its immediate electronic environment. This effect propagates through the intervening bonds and affects the electronic environments of NMR-active nuclei up to three bonds away; occasionally, even farther. This phenomenon is called spin–spin coupling or J-coupling. Coupling interactions are mutual and result in small changes in the absorption frequencies of both nuclei involved. While nuclei of the same element are involved...
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Spin–Spin Coupling: One-Bond Coupling01:17

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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–Spin Coupling Constant: Overview01:08

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

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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...
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Spin–Spin Coupling: Three-Bond Coupling (Vicinal Coupling)01:22

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

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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.
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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Molecules and Compounds02:38

Molecules and Compounds

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Atoms and Molecules
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Monolayer Contact Doping of Silicon Surfaces and Nanowires Using Organophosphorus Compounds
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Li doped kagome spin liquid compounds.

Wei Jiang1, Huaqing Huang, Jia-Wei Mei

  • 1Department of Materials Science and Engineering, University of Utah, Salt Lake City, Utah 84112, USA. fliu@eng.utah.edu.

Physical Chemistry Chemical Physics : PCCP
|August 14, 2018
PubMed
Summary
This summary is machine-generated.

Lithium doping herbertsmithite and Zn-doped barlowite, kagome spin liquids, results in an insulating state, not exotic metallic states. This is due to charge transfer and electron trapping, contrary to prior theories.

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Area of Science:

  • Condensed Matter Physics
  • Materials Science
  • Quantum Magnetism

Background:

  • Two-dimensional kagome spin liquids are candidates for realizing exotic quantum states.
  • Charge doping quantum spin liquids theoretically predicts metallic states, including high-temperature superconductivity.
  • Experimental Li-doping of herbertsmithite yielded an insulating state, contradicting theoretical predictions.

Purpose of the Study:

  • Investigate the effects of lithium (Li) intercalation doping on herbertsmithite and Zn-doped barlowite.
  • Explain the experimentally observed insulating behavior in Li-doped herbertsmithite.
  • Determine if Li doping can lead to exotic metallic states in these kagome spin liquid compounds.

Main Methods:

  • First-principles calculations were employed to study Li intercalation doping.
  • Optimized Li positions within the crystal structures were identified.
  • Analysis of charge distribution and chemical bonding was performed.

Main Results:

  • The optimized Li position in herbertsmithite was identified as the Cl-(OH)3-Cl pentahedron site.
  • Increasing Li doping concentration led to a linear decrease in saturation magnetization due to charge transfer from Li to Cu ions.
  • Li doping formed chemical bonds with (OH)- and Cl- ions, localizing charge and causing an insulating state, consistent with experimental findings.

Conclusions:

  • Lithium doping of herbertsmithite and Zn-doped barlowite kagome spin liquids results in insulating states, not the predicted exotic metallic states.
  • The insulating behavior is attributed to charge transfer and electron trapping induced by Li intercalation.
  • Alternative doping strategies, such as element substitution, are necessary to explore exotic metallic states in these materials.