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関連する概念動画

Spin–Spin Coupling Constant: Overview01:08

Spin–Spin Coupling Constant: Overview

964
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...
964
Spin–Spin Coupling: Three-Bond Coupling (Vicinal Coupling)01:22

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

1.1K
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...
1.1K
Molecular Shape and Polarity03:37

Molecular Shape and Polarity

60.7K
Dipole Moment of a Molecule
60.7K
Spin–Spin Coupling: One-Bond Coupling01:17

Spin–Spin Coupling: One-Bond Coupling

1.0K
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,...
1.0K
Chemical Shift: Internal References and Solvent Effects01:17

Chemical Shift: Internal References and Solvent Effects

684
In an NMR sample, precise measurement of the absolute absorption frequencies of nuclei is difficult. A standard internal reference compound is added, and the frequency difference between the reference signal and sample signals is measured.
The internal reference compound generally used in NMR spectroscopy is tetramethylsilane (TMS). TMS is preferred because it is chemically inert, soluble in NMR solvents, and easily removable. Also, the highly shielded methyl protons in TMS yield an intense...
684
Spin–Spin Coupling: Two-Bond Coupling (Geminal Coupling)01:20

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

1.1K
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...
1.1K

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関連する実験動画

Updated: Jul 27, 2025

Vibrational Spectra of a N719-Chromophore/Titania Interface from Empirical-Potential Molecular-Dynamics Simulation, Solvated by a Room Temperature Ionic Liquid
08:54

Vibrational Spectra of a N719-Chromophore/Titania Interface from Empirical-Potential Molecular-Dynamics Simulation, Solvated by a Room Temperature Ionic Liquid

Published on: January 25, 2020

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振動力強い結合下での溶媒の極性

Maciej Piejko1, Bianca Patrahau1, Kripa Joseph1

  • 1University of Strasbourg, CNRS, ISIS and icFRC, 8 Allée Gaspard Monge, 67000 Strasbourg, France.

Journal of the American Chemical Society
|June 8, 2023
PubMed
まとめ

振動性強い結合は分散力に影響して溶媒の極性を変化させる. この発見は 化学反応や溶媒の性質に この量子効果がどう影響するかに 新しい洞察を与えてくれます

科学分野:

  • 量子化学について
  • 物理化学
  • スペクトロスコーピー

背景:

  • 振動強い結合 (VSC) は,光学腔モードによる分子振動のハイブリッド化を含みます.
  • VSCは化学反応速度と選択性に影響することが知られているが,その背後にあるメカニズムは完全に理解されていない.
  • 溶媒の極性は化学反応に影響する重要な要因である.

研究 の 目的:

  • 溶媒の極性に対するVSCの影響を調査する.
  • 溶媒の性質を変化させるVSCの役割と分散力との関連を解明する.

主な方法:

  • 溶媒の極性変化を定量化するために,敏感なソルバトクロミックプローブであるライハルトの染料 (RD) を利用した.
  • アルコール溶剤の振動帯を光学空洞モードと結合してVSCを使用します.
  • VSCへの反応としてRDの最大吸収の変化を測定した.

主要な成果:

  • VSCによるRDの最大吸収 (~15.1 nm,5.1 kJ·mol-1まで) の有意な赤色偏移が観察されました.
  • 極性変化の大きさは,アルキル鎖の長さ,分子表面積,およびアリファティックアルコールにおける極性度と相関していることが判明した.
  • 真空の変動から生じる分散力にVSCが影響することを実証した.

さらに関連する動画

Spatial Separation of Molecular Conformers and Clusters
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Spatial Separation of Molecular Conformers and Clusters

Published on: January 9, 2014

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Covalent Attachment of Single Molecules for AFM-based Force Spectroscopy
10:37

Covalent Attachment of Single Molecules for AFM-based Force Spectroscopy

Published on: March 16, 2020

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関連する実験動画

Last Updated: Jul 27, 2025

Vibrational Spectra of a N719-Chromophore/Titania Interface from Empirical-Potential Molecular-Dynamics Simulation, Solvated by a Room Temperature Ionic Liquid
08:54

Vibrational Spectra of a N719-Chromophore/Titania Interface from Empirical-Potential Molecular-Dynamics Simulation, Solvated by a Room Temperature Ionic Liquid

Published on: January 25, 2020

5.7K
Spatial Separation of Molecular Conformers and Clusters
10:37

Spatial Separation of Molecular Conformers and Clusters

Published on: January 9, 2014

9.0K
Covalent Attachment of Single Molecules for AFM-based Force Spectroscopy
10:37

Covalent Attachment of Single Molecules for AFM-based Force Spectroscopy

Published on: March 16, 2020

9.7K

結論:

  • VSCは明らかに溶媒の極性を変化させる.
  • 観測された極性の変化は,強い結合下での分散相互作用の修正と関連しています.
  • 分散相互作用は,VSCが化学プロセスに影響を与える重要な媒介物として提案されています.