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相关概念视频

¹H NMR: Interpreting Distorted and Overlapping Signals01:02

¹H NMR: Interpreting Distorted and Overlapping Signals

989
Spin systems where the difference in chemical shifts of the coupled nuclei is greater than ten times J are called first-order spin systems. These nuclei are weakly coupled, and their chemical shifts and coupling constant can generally be estimated from the well-separated signals in the spectrum.
As Δν decreases and the signals move closer, the doublets appear increasingly distorted. The intensities of the inner lines increase at the cost of those of the outer lines as the signals are...
989
Spin–Spin Coupling: One-Bond Coupling01:17

Spin–Spin Coupling: One-Bond Coupling

922
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,...
922
Spin–Spin Coupling Constant: Overview01:08

Spin–Spin Coupling Constant: Overview

862
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...
862
Spin–Spin Coupling: Two-Bond Coupling (Geminal Coupling)01:20

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

939
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...
939
Spin–Spin Coupling: Three-Bond Coupling (Vicinal Coupling)01:22

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

1.0K
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...
1.0K
NMR Spectroscopy: Spin–Spin Coupling01:08

NMR Spectroscopy: Spin–Spin Coupling

1.2K
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...
1.2K

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相关实验视频

Updated: May 24, 2025

Excitonic Hamiltonians for Calculating Optical Absorption Spectra and Optoelectronic Properties of Molecular Aggregates and Solids
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在多对线方法中使用非对线函数的旋转翻转TDDFT的分析梯度.

Hao Li1, Qiming Sun2, Yi Qin Gao1

  • 1College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, the People's Republic of China.

Journal of chemical theory and computation
|March 5, 2025
PubMed
概括

本研究引入了一种稳定的方法,用于计算使用非对线函数的旋转转时间依赖密度函数理论 (TDDFT) 梯度. 这一进步使得精确的几何优化和对激发状态的计算成为可能,改进了计算化学方法.

科学领域:

  • 量子化学 是一个量子化学.
  • 计算化学的计算化学
  • 理论化学 理论化学

背景情况:

  • 旋转翻转时间依赖密度函数理论 (SF-TDDFT) 对具有多配置性质的系统至关重要.
  • 当前的对直线函数实现面临着局限性.
  • 非对线函数提供了更好的对称性和退化保存,但也带来了数值挑战.

研究的目的:

  • 开发和验证非线性旋转翻转TDDFT的分析梯度.
  • 为应对非对线函数的第三阶导数计算的挑战.
  • 为了实现精确的几何优化和激发状态属性计算.

主要方法:

  • 对SF-TDDFT分析梯度的多线性方法的应用.
  • 对一般化梯度近似 (GGA) 和元-GGA函数的第三阶导数的计算.
  • 通过比较分析和数值梯度的基准测试进行验证.

主要成果:

  • 成功地实现了对非对线性SF-TDDFT的数值稳定的分析梯度.
  • 对数值梯度和自旋保护状态的验证.
  • 在几何优化和激发状态能量计算中的应用的演示.

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Site Directed Spin Labeling and EPR Spectroscopic Studies of Pentameric Ligand-Gated Ion Channels
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Spin Saturation Transfer Difference NMR SSTD NMR: A New Tool to Obtain Kinetic Parameters of Chemical Exchange Processes
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相关实验视频

Last Updated: May 24, 2025

Excitonic Hamiltonians for Calculating Optical Absorption Spectra and Optoelectronic Properties of Molecular Aggregates and Solids
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Spin Saturation Transfer Difference NMR SSTD NMR: A New Tool to Obtain Kinetic Parameters of Chemical Exchange Processes
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Spin Saturation Transfer Difference NMR SSTD NMR: A New Tool to Obtain Kinetic Parameters of Chemical Exchange Processes

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结论:

  • 多线性方法为非线性SF-TDDFT提供了稳定的分析梯度.
  • 这种方法可方便精确计算激发状态和分子性质.
  • 开发的梯度是TDDFT和分子动力学进一步进步的基础.