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相关概念视频

Radical Reactivity: Intramolecular vs Intermolecular01:33

Radical Reactivity: Intramolecular vs Intermolecular

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Radical reactions can occur either intermolecularly or intramolecularly. In an intermolecular radical reaction, a nucleophilic radical adds to an electrophilic alkene or vice versa. In such reactions, the radical and generally the alkene, which is also called the radical trap, are two different molecules. Additionally, for such intermolecular reactions to occur, the radical trap must be active, present in an excess concentration, and the radical starting material must have a weak...
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Radical Reactivity: Overview01:11

Radical Reactivity: Overview

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Radicals, the highly reactive species, gain stability by undergoing three different reactions. The first reaction involves a radical-radical coupling, in which a radical combines with another radical, forming a spin‐paired molecule. The second reaction is between a radical and a spin‐paired molecule, generating a new radical and a new spin‐paired molecule. The third reaction is radical decomposition in a unimolecular reaction, forming a new radical and a spin‐paired...
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Radicals: Electronic Structure and Geometry01:07

Radicals: Electronic Structure and Geometry

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This lesson delves into the geometry of a radical, which is influenced by the electronic structure of the molecule. The principle is similar to that of a lone pair, where the unpaired electron influences the geometry at the radical center.
Accordingly, the structure of a trivalent radical lies between the geometries of carbocations and carbanions. An sp2-hybridized carbocation is trigonal planar, while an sp3-hybridized carbanion is trigonal pyramidal. Here, the difference in geometry is...
4.1K
Valence Bond Theory02:42

Valence Bond Theory

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Coordination compounds and complexes exhibit different colors, geometries, and magnetic behavior, depending on the metal atom/ion and ligands from which they are composed. In an attempt to explain the bonding and structure of coordination complexes, Linus Pauling proposed the valence bond theory, or VBT, using the concepts of hybridization and the overlapping of the atomic orbitals. According to VBT, the central metal atom or ion (Lewis acid) hybridizes to provide empty orbitals of suitable...
8.7K
Radical Formation: Overview01:03

Radical Formation: Overview

2.1K
A bond can be broken either by heterolytic bond cleavage to form ions or homolytic bond cleavage to yield radicals. A fishhook arrow is used to represent the motion of a single electron in homolytic bond cleavage. There are two main sources from which radicals can be formed:
Radicals from spin-paired molecules:
Radicals can be obtained from spin-paired molecules either by homolysis or electron transfer. While two radicals are formed in the former, an electron is added in the...
2.1K
Radical Formation: Addition00:47

Radical Formation: Addition

1.7K
Radicals can be formed by adding a radical to a spin-paired molecule. This is typically observed with unsaturated species, where the addition of a radical across the π bond leads to the production of a new radical by dissolving the π bond. For example, the addition of a Br radical to an alkene yields a carbon-centered radical.
Similar to charge conservation in chemical reactions, spin conservation is implicit for radical reactions. Accordingly, the product formed must possess an...
1.7K

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高旋转的布拉特的三根学说

Rishu Khurana1, Ashima Bajaj1, K R Shamasundar2

  • 1Institute of Nano Science and Technology, Sector-81, Mohali, Punjab 140306, India.

The journal of physical chemistry. A
|August 25, 2023
PubMed
概括

这项研究准确地计算了有机三根子中的能量差距,这对于分子磁铁和自旋电子学至关重要. 先进的计算方法证实了四重奏的基本状态,与实验发现保持一致.

科学领域:

  • 量子化学是一种量子化学.
  • 材料科学是一种材料科学.
  • 有机化学 有机化学

背景情况:

  • 有机三根与四方基本状态的有机三根是分子磁铁和旋转电子学的关键.
  • 之前的破坏对称度DFT (BS-DFT) 方法与实验相比,高估了能量差距.
  • 布拉特的基于根的三根表现出低的双重状态和四个基本状态.

研究的目的:

  • 准确计算一个布拉特的根基的三根基的双重四重奏能量差距.
  • 调查和改进传统的BS-DFT限制.
  • 为实验合成提出并以计算方式建模新的三根数.

主要方法:

  • 采用了各种 *ab initio* 方法,包括旋转约束断对称 DFT (CBS-DFT).
  • 利用状态平均的CASSCF和NEVPT2计算来解决旋转污染和多引用问题.
  • 使用一系列活跃空间进行计算,以获得高精度.

主要成果:

  • 计算的能量差距显示与实验值有很强的一致性,克服了BS-DFT的高估值.
  • 确认了原型三基和两种新提出的类型的四基基本状态.
  • 证明了先进的 *ab initio* 方法的有效性,用于准确的电子结构确定.

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结论:

  • 精确的 * ab initio * 方法为有机三根分子提供可靠的能量差值.
  • 研究的三根子,包括新的设计,拥有适合高级应用的四方基态.
  • 计算建模对于指导新型高旋转分子的实验合成和表征至关重要.