在双兰化物合的团中,双芳香和逆三明治结构:从f电子到d电子的激发
Xun-Jie Mei1, Huai-Qian Wang1,2, Jia-Ming Zhang2
1College of Engineering, Huaqiao University, Quanzhou 362021, China.
The journal of physical chemistry. A
|April 29, 2025
概括
由于f→d电子激发,在n=9时形成的双兰化物合的团中的反向三明治结构. 这种独特的结合使双重芳香度成为可能,但能量损耗会在n=10.0时引起结构转变.
科学领域:
- 计算化学计算化学
- 材料科学 材料科学 材料科学
- 无机化学 无机化学 有机化学
背景情况:
- 用兰化物合的团因其独特的电子和结构性质而引起人们的兴趣.
- 了解特定集群几何学的形成机制,如反向三明治结构,对于材料设计至关重要.
研究的目的:
- 阐明双胺合团 (M2B10−,M = La,Ce,Pr,Nd) 中逆三明治结构的大小依赖的形成机制.
- 调查控制集群稳定性和芳香性的几何和电子特性.
主要方法:
- 密度函数理论 (DFT) 的计算被用来优化结构和研究电子性质.
- 适应性自然密度分区 (AdNDP) 分析被用来发现结合机制.
- 对不同集群大小 (n=9和n=10) 进行了比较研究.
主要成果:
- 在n=9的M2B10−星团中预测了反向三明治配置,理论的结合能量与实验数据很好地一致.
- 确定了一种涉及f → d电子激发在兰坦化物中的新型结合机制,形成定向的d-p δ键.
- 这些集群表现出双重芳香度 (σ-和π-芳香度),这是兰化物合集群中首次出现的.
- 一个刺激诱导的电子配置影响旋转的多重性,并减少约束能量,解释了在n=10.0时向常规几何体的过渡.
结论:
- 在双兰他化物系统中逆三明治稳定性的临界大小是n=9.
- f → d电子刺激是形成逆三明治结构和实现双重芳香度的关键.
- 建议制定一个一般的电子设计规则,用于量身定制重金属合剂集群中的芳香度.
更多相关视频
08:04Excitonic Hamiltonians for Calculating Optical Absorption Spectra and Optoelectronic Properties of Molecular Aggregates and Solids
Published on: May 27, 2020
8.3K
10:10Application of Elemental Lanthanides in the Selective C-F Activation of Trifluoromethylated Benzofulvenes Providing Access to Various Difluoroalkenes
Published on: July 28, 2018
6.4K
相关概念视频
04:01VSEPR Theory and the Effect of Lone Pairs
41.4K
Effect of Lone Pairs of Electrons on Molecule Geometry
41.4K
02:42Valence Bond Theory
8.3K
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...
8.3K
02:55Exceptions to the Octet Rule
27.1K
Many covalent molecules have central atoms that do not have eight electrons in their Lewis structures. These molecules fall into three categories:
27.1K
02:52Resonance
51.8K
The Lewis structure of a nitrite anion (NO2−) may actually be drawn in two different ways, distinguished by the locations of the N-O and N=O bonds.
51.8K
03:24Hybridization of Atomic Orbitals I
45.5K
The mathematical expression known as the wave function, ψ, contains information about each orbital and the wavelike properties of electrons in an isolated atom. When atoms are bound together in a molecule, the wave functions combine to produce new mathematical descriptions that have different shapes. This process of combining the wave functions for atomic orbitals is called hybridization and is mathematically accomplished by the linear combination of atomic orbitals. The new orbitals that...
45.5K
02:16Resonance and Hybrid Structures
16.2K
According to the theory of resonance, if two or more Lewis structures with the same arrangement of atoms can be written for a molecule, ion, or radical, the actual distribution of electrons is an average of that shown by the various Lewis structures.
Resonance Structures and Resonance Hybrids
The Lewis structure of a nitrite anion (NO2−) may actually be drawn in two different ways, distinguished by the locations of the N–O and N=O bonds.
Resonance Structures and Resonance Hybrids
The Lewis structure of a nitrite anion (NO2−) may actually be drawn in two different ways, distinguished by the locations of the N–O and N=O bonds.
16.2K