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¹H NMR: Long-Range Coupling01:27

¹H NMR: Long-Range Coupling

1.7K
The coupling interactions of nuclei across four or more bonds are usually weak, with J values less than 1 Hz. While these are usually not observed in spectra, the presence of multiple bonds along the coupling pathway can result in observable long-range coupling.
In alkenes, spin information is communicated via σ–π overlap, as seen in allylic (four-bond) and homoallylic (five-bond) couplings. These coupling interactions are stronger when the σ bond is parallel to the alkene...
1.7K
¹H NMR: Interpreting Distorted and Overlapping Signals01:02

¹H NMR: Interpreting Distorted and Overlapping Signals

998
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...
998
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
Spin–Spin Coupling: Two-Bond Coupling (Geminal Coupling)01:20

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

946
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...
946
¹H NMR Signal Multiplicity: Splitting Patterns01:13

¹H NMR Signal Multiplicity: Splitting Patterns

4.9K
When protons A and X are coupled, their nuclear spin energy levels are slightly modified. This is because the energy required to excite proton A to a spin state parallel to proton X is slightly different from the energy required for it to become anti-parallel to spin X. Consequently, there are two possible excitation frequencies for A (A1 and A2), depending on the spin state of X, and vice versa. The mutual nature of coupling implies that the difference between frequencies A1 and A2, indicated...
4.9K
Double Resonance Techniques: Overview01:12

Double Resonance Techniques: Overview

185
Double resonance techniques in Nuclear Magnetic Resonance (NMR) spectroscopy involve the simultaneous application of two different frequencies or radiofrequency pulses to manipulate and observe two distinct nuclear spins. One important application of double resonance is spin decoupling, which selectively suppresses coupling with one type of nucleus while observing the NMR signal from another nucleus, simplifying the spectrum and enhancing resolution.
Spin decoupling is usually achieved by...
185

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相关实验视频

Updated: May 29, 2025

Methods of Ex Situ and In Situ Investigations of Structural Transformations: The Case of Crystallization of Metallic Glasses
08:55

Methods of Ex Situ and In Situ Investigations of Structural Transformations: The Case of Crystallization of Metallic Glasses

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分析核梯度和衍生合理论用于多参考扰动方法.

Jae Woo Park1

  • 1Department of Chemistry, Chungbuk National University (CBNU), Cheongju 28644, Korea. jaewoopark@cbnu.ac.kr.

Physical chemistry chemical physics : PCCP
|February 3, 2025
PubMed
概括

准确的量子化学需要电子相关性. 本文详细介绍了使用多引用扰动理论 (MRPT) 进行高效的几何优化和动力学模拟的分析梯度理论和方法.

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:

  • 电子相关性对于精确的能量和波函数量子化学计算至关重要.
  • 多配置方法使用电子配置的线性组合来描述静态相关性.
  • 动态相关性可以使用多配置参考函数进行校正.

研究的目的:

  • 为分析梯度理论提供全面的综述.
  • 讨论使用多引用扰乱理论 (MRPT) 获得分析梯度和衍生合的方法.
  • 审查非adiabatic动态模拟中的实际应用.

主要方法:

  • 分析梯度理论的审查.
  • 讨论使用MRPTs计算分析梯度和导数合的方法.
  • 探索用于高效梯度和合计算的算法.

主要成果:

  • 最近使用MRPTs开发了分析梯度和衍生合的高效算法.
  • 详细审查这些方法的特性.
  • 概述它们在非adiabatic动态中的应用.

结论:

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  • 使用MRPT的分析梯度和衍生合方法对于先进的量子化学应用至关重要.
  • 这些方法促进了几何优化和动态模拟.
  • 这篇评论为利用这些强大的计算工具提供了一份指南.