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相关概念视频

¹H NMR: Long-Range Coupling01:27

¹H NMR: Long-Range Coupling

1.8K
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...
1.8K
¹H NMR: Interpreting Distorted and Overlapping Signals01:02

¹H NMR: Interpreting Distorted and Overlapping Signals

1.0K
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...
1.0K
Spin–Spin Coupling: Two-Bond Coupling (Geminal Coupling)01:20

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

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

Spin–Spin Coupling: One-Bond Coupling

990
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,...
990
¹H NMR: Complex Splitting01:13

¹H NMR: Complex Splitting

1.3K
A proton M that is coupled to a proton X results in doublet signals for M. However, NMR-active nuclei can be simultaneously coupled to more than one nonequivalent nucleus. When M is coupled to a second proton A, such as in styrene oxide, each peak in the doublet is split into another doublet.
Splitting diagrams or splitting tree diagrams are routinely used to depict such complex couplings. While drawing splitting diagrams, the splitting with the larger coupling constant is usually applied...
1.3K
Hybridization of Atomic Orbitals II03:35

Hybridization of Atomic Orbitals II

32.3K
sp3d and sp3d 2 Hybridization
32.3K

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Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry
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结合集群密度为基础的多体扩张.

Kevin Focke1, Christoph R Jacob1

  • 1Institute of Physical and Theoretical Chemistry, Technische Universität Braunschweig, Gaußstraße 17, 38106 Braunschweig, Germany.

The journal of physical chemistry. A
|October 23, 2023
PubMed
概括

一种新的基于密度的多体膨胀方法显著降低了高精度合集群计算的计算成本. 这种方法实现了水的化学精度,使复杂的分子模拟更可行.

科学领域:

  • 计算化学计算化学
  • 量子化学 是一个量子化学.
  • 分子建模分子建模

背景情况:

  • 配对集群与单元和双元和扰动三元 (CCSD(T)) 是准确的分子电子结构计算的黄金标准.
  • CCSD (T) 的N^7计算缩放严重限制了它对大型分子系统的应用.

研究的目的:

  • 开发和评估一种资源高效的方法,用于对大型分子系统进行准确的CCSDT计算.
  • 为了评估基于密度的多体膨胀与CCSD一起的性能.

主要方法:

  • 应用基于密度的多体膨胀方法与CCSD结合使用.
  • 对中性,质子化和质子化水六合体以及 (H2O) 16和 (H2O) 17集群的准确性评估.
  • 与传统的基于能量的多体扩张进行比较,并研究密度近似效应 (哈特里-福克与合集群密度).

主要成果:

  • 基于密度的两体膨胀实现了中性水集群的化学精度 (4kJ/mol) 内的CCSDT能量.
  • 这种精度超过了传统的基于能源的三体扩张.
  • 即使使用Hartree-Fock密度而不是合集群密度,也保持了准确性.

结论:

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  • 基于密度的多体扩展提供了一个计算效率高且可并行实现的替代方案,可以实现CCSD (T) 质量的结果.
  • 这种方法显著扩大了大型和复杂的分子系统高精度电子结构计算的可行性.