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相关概念视频

Atomic Nuclei: Nuclear Spin State Population Distribution01:14

Atomic Nuclei: Nuclear Spin State Population Distribution

974
Near absolute zero temperatures, in the presence of a magnetic field, the majority of nuclei prefer the lower energy spin-up state to the higher energy spin-down state. As temperatures increase, the energy from thermal collisions distributes the spins more equally between the two states. The Boltzmann distribution equation gives the ratio of the number of spins predicted in the spin −½ (N−) and spin +½ (N+) states.
974
Atomic Nuclei: Nuclear Relaxation Processes01:23

Atomic Nuclei: Nuclear Relaxation Processes

649
In the absence of an external magnetic field, nuclear spin states are degenerate and randomly oriented. When a magnetic field is applied, the spins begin to precess and orient themselves along (lower energy) or against (higher energy) the direction of the field. At equilibrium, a slight excess population of spins exists in the lower energy state. Because the direction of the magnetic field is fixed as the z-axis,  the precessing magnetic moments are randomly oriented around the z-axis.
649
Atomic Nuclei: Nuclear Spin State Overview01:03

Atomic Nuclei: Nuclear Spin State Overview

938
NMR-active nuclei have energy levels called 'spin states' that are associated with the orientations of their nuclear magnetic moments. In the absence of a magnetic field, the nuclear magnetic moments are randomly oriented, and the spin states are degenerate. When an external magnetic field is applied, the spin states have only 2 + 1 orientations available to them. A proton with = ½ has two available orientations. Similarly, for a quadrupolar nucleus with a nuclear spin value of...
938
Atomic Nuclei: Nuclear Spin01:08

Atomic Nuclei: Nuclear Spin

1.9K
All atomic particles possess an intrinsic angular momentum, or 'spin'. Electrons, protons, and neutrons each have a spin value of ½, although protons and neutrons in nuclei may have higher half-integer spins owing to energetic factors.
Atomic nuclei have a net nuclear spin, , which can have an integer or half-integer value. In atomic nuclei, the spins of protons are paired against each other but not with neutrons, and vice versa. Consequently, an even number of protons does not...
1.9K
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
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

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相关实验视频

Updated: Jun 28, 2025

Excitonic Hamiltonians for Calculating Optical Absorption Spectra and Optoelectronic Properties of Molecular Aggregates and Solids
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对于完整的活性空间的分析核梯度 线性化的对密度函数理论

Matthew R Hennefarth1, Matthew R Hermes1, Donald G Truhlar2

  • 1Department of Chemistry and Chicago Center for Theoretical Chemistry, University of Chicago, Chicago, Illinois 60637, United States.

Journal of chemical theory and computation
|April 19, 2024
PubMed
概括

本研究介绍了线性对密度函数理论 (L-PDFT) 的分析梯度,这是一种用于建模复杂光化学反应的成本效益高的方法. 这些梯度准确地预测了各种分子的分子几何和激发能.

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科学领域:

  • 计算化学的计算化学
  • 量子化学 是一个量子化学.
  • 摄影化学的使用

背景情况:

  • 由于形交叉点和多配置激发状态,模拟光化学反应具有挑战性.
  • 精确的潜在能量表面计算需要具有状态相互作用的多态方法.
  • 传统的多引用方法在计算上昂贵.

研究的目的:

  • 为线性化的对密度函数理论 (L-PDFT) 推导和实现分析梯度.
  • 为了证明L-PDFT梯度在预测分子性质方面的实用性.
  • 为准确的兴奋状态计算提供一个具有成本效益的替代方案.

主要方法:

  • 对L-PDFT的分析梯度的导出.
  • 在PySCF-forge软件中实现L-PDFT梯度.
  • 适用于甲,s-trans-butadiene,和细胞素.

主要成果:

  • 成功推导和实施L-PDFT分析梯度.
  • 准确预测基本状态和兴奋状态平衡几何.
  • 可靠的计算的亚亚巴斯激发能量.

结论:

  • 具有分析梯度的L-PDFT是研究光化学反应的强大且具有成本效益的工具.
  • 该方法准确地模拟了具有强大的核电子合的潜在能量表面.
  • 这一进步有助于更准确地预测激发状态下的分子行为.