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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

1.1K
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...
1.1K
NMR Spectroscopy: Spin–Spin Coupling01:08

NMR Spectroscopy: Spin–Spin Coupling

1.6K
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...
1.6K
¹³C NMR: ¹H–¹³C Decoupling01:04

¹³C NMR: ¹H–¹³C Decoupling

1.2K
The probability of having two carbon-13 atoms next to each other is negligible because of the low natural abundance of carbon-13. Consequently, peak splitting due to carbon-carbon spin-spin coupling is not observed in spectra. However, protons up to three sigma bonds away split the carbon signal according to the n+1 rule, resulting in complicated spectra.
A broadband decoupling technique is used to simplify these complex, sometimes overlapping, signals. Broadband decoupling relies on a...
1.2K
¹³C NMR: Distortionless Enhancement by Polarization Transfer (DEPT)01:20

¹³C NMR: Distortionless Enhancement by Polarization Transfer (DEPT)

1.2K
When proton-coupled carbon-13 spectra are simplified by a broadband proton decoupling technique, structural information about the coupled protons is lost. Distortionless enhancement by polarization transfer (DEPT) is a technique that provides information on the number of hydrogens attached to each carbon in a molecule. While the DEPT experiment utilizes complex pulse sequences, the pulse delay and flip angle are specifically manipulated. The resulting signals have different phases depending on...
1.2K
Spin–Spin Coupling: Two-Bond Coupling (Geminal Coupling)01:20

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

1.2K
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...
1.2K
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

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Experimental Methods for Spin- and Angle-Resolved Photoemission Spectroscopy Combined with Polarization-Variable Laser
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使用DFT/CIS方法与旋转轨道合计算L和M边的光谱.

Aniket Mandal1, John M Herbert1

  • 1Department of Chemistry & Biochemistry, The Ohio State University, Columbus, Ohio 43210, USA. herbert@chemistry.ohio-state.edu.

Physical chemistry chemical physics : PCCP
|July 21, 2025
PubMed
概括
此摘要是机器生成的。

旋转轨道分裂对于建模L边缘光谱至关重要. 使用密度功能理论配置-相互作用单元 (DFT/CIS) 的新型,具有成本效益的工具,准确计算核心层次的光谱,包括旋转轨道效应.

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科学领域:

  • 计算化学的计算化学
  • 频谱学是一种光谱学.
  • 量子力学就是量子力学.

背景情况:

  • 建模X射线光谱,特别是L边缘光谱,需要考虑2p轨道的旋转轨道分裂.
  • 准确计算核心层次光谱对于理解电子结构至关重要.

研究的目的:

  • 引入一个低成本的计算工具来计算核心层次的光谱,特别是针对L边缘的光谱.
  • 将旋转轨道分裂效应纳入核心层次光谱的计算.

主要方法:

  • 结合了布雷特-保利哈密尔顿的旋转轨道平均场描述与来自半实证密度函数理论配置-相互作用单元 (DFT/CIS) 方法的非相对论激发状态.
  • 使用状态交互方法和对核心轨道能量进行半经验性校正,减少对特设转移的需求.
  • 采用核心/值分离近似和旋转轨道合.

主要成果:

  • 用自旋轨道合的DFT/CIS方法,以较低的计算成本提供半定量L边谱.
  • 旋转轨道合显著影响计算的光谱,正如对3D过渡金属和主要组化合物所证明的那样.
  • 发现旋转轨道分裂对3D过渡金属物种的M边谱具有微不足道的影响.

结论:

  • 开发的DFT/CIS方法提供了一个计算效率高,准确的方法来建模L边缘光谱.
  • 包括旋转轨道合对于在L-边缘光谱计算中的定性协议至关重要.
  • 该工具通过使用不同的活跃轨道空间来促进光谱分配.