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相关概念视频

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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相关实验视频

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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在振动强合下溶剂极性

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
概括

振动强通过影响分散力改变溶剂极性. 这一发现为量子效应如何影响化学反应和溶剂特性提供了新的见解.

科学领域:

  • 量子化学
  • 物理化学
  • 光谱学

背景情况:

  • 振动强 (VSC) 涉及分子振动与光腔模式的混合.
  • 已知VSC会影响化学反应速率和选择性,但根本的机制尚未完全理解.
  • 溶剂极性是影响化学反应的关键因素.

研究的目的:

  • 调查VSC对溶剂极性的影响.
  • 阐明VSC在改变溶剂性质中的作用及其与分散力的联系.

主要方法:

  • 使用Richardt染料 (RD),一个灵敏的solvatochromic探针,以量化溶剂极性变化.
  • 通过将酒精溶剂的OH和CH振动带与光腔模式结合使用VSC.
  • 测量RD的最大吸收变化作为VSC的反应.

主要成果:

  • 由于VSC,在RD的最大吸收值中观察到显著的红移 (高达~15.1 nm,5.1 kJ·mol-1).
  • 发现极性变化的大小与链长度,分子表面积和性醇的极性化相关.
  • 证明VSC会影响来自真空波动的分散力.

结论:

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Covalent Attachment of Single Molecules for AFM-based Force Spectroscopy

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  • 可以证明VSC改变了溶剂的极性.
  • 观察到的极性变化与强合下的分散相互作用的变化有关.
  • 分散相互作用被认为是通过VSC影响化学过程的关键媒介.