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相关概念视频

Spin–Spin Coupling Constant: Overview01:08

Spin–Spin Coupling Constant: Overview

1.0K
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...
1.0K
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
Spin–Spin Coupling: One-Bond Coupling01:17

Spin–Spin Coupling: One-Bond Coupling

1.1K
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,...
1.1K
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
Singularity Functions for Shear01:26

Singularity Functions for Shear

193
In structural analysis, singularity functions are crucial in simplifying the representation of shear forces in beams under discontinuous loading. These functions describe discontinuous  variations in shear force across a beam with varying loads by using a single mathematical expression, regardless of the complexity of the loading conditions. The singularity functions are derived from creating a free-body diagram of the beam and then making conceptual cuts at specific points to examine the...
193
Radicals: Electronic Structure and Geometry01:07

Radicals: Electronic Structure and Geometry

4.2K
This lesson delves into the geometry of a radical, which is influenced by the electronic structure of the molecule. The principle is similar to that of a lone pair, where the unpaired electron influences the geometry at the radical center.
Accordingly, the structure of a trivalent radical lies between the geometries of carbocations and carbanions. An sp2-hybridized carbocation is trigonal planar, while an sp3-hybridized carbanion is trigonal pyramidal. Here, the difference in geometry is...
4.2K

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Updated: Sep 10, 2025

Spin Saturation Transfer Difference NMR SSTD NMR: A New Tool to Obtain Kinetic Parameters of Chemical Exchange Processes
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单元二根子的旋转密度功能调整

Yi Shi1, Yuming Shi2, Adam Wasserman3,4

  • 1State Key Laboratory for Artificial Microstructure and Mesoscopic Physics, Frontier Science Center for Nano-optoelectronics and School of Physics, Peking University, Beijing 100871, People's Republic of China.

Journal of chemical theory and computation
|August 22, 2025
PubMed
概括
此摘要是机器生成的。

一种新的自旋密度函数规范化 (SR) 方法纠正了单点二根的断对称密度函数理论 (DFT) 计算中的错误. 这种方法可以准确地预测复杂反应的能量障碍,如环丁自动化.

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科学领域:

  • 量子化学
  • 计算化学
  • 理论化学

背景情况:

  • 破碎对称密度函数理论 (DFT) 广泛用于单点二根的静态相关性.
  • 这种方法对于复杂的电子结构可能会因为人造的旋转对称性破裂而失败.
  • 单点二极点来自 (准) 退化的边界轨道.

研究的目的:

  • 开发一种方法来纠正破碎对称性DFT中的人工对称性破坏.
  • 提高复杂电子结构系统的能量计算的准确性.

主要方法:

  • 引入一个旋转密度功能规范化 (SR) 方法.
  • 在分区密度函数理论 (PDFT) 的框架内集成SR.
  • 用于自动化循环丁,一个具有单基转换状态的系统.

主要成果:

  • 这种SR-PDFT方法有效地纠正了人工对称性破坏造成的错误.
  • 传统的破坏对称度DFT计算低估了自动化过渡状态能量.
  • 在自动化反应中,SR-PDFT可产生化学精确的阻隔高度.

结论:

  • SR-PDFT 方法提供了一种可靠的方法来处理单点二根的静态相关性.
  • 这种方法克服了复杂系统的传统失对称DFT的局限性.
  • 可以准确预测反应屏障高度,证明该方法的有效性.