含有异原子的芳香化合物在石墨上的相互作用能量和稳定性
Yoshihiro Kikkawa1, Seiji Tsuzuki2
1National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba Central 5, 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan. y.kikkawa@aist.go.jp.
Physical chemistry chemical physics : PCCP
|March 3, 2026
概括
含有异原子的芳香化合物 (HAC) 呈现与多环芳香 (PAH) 相似的 π-π 堆叠相互作用. 这些相互作用对于自组装系统至关重要,分散力主导着对石墨表面的吸引力.
科学领域:
- 材料科学 材料科学 材料科学
- 计算化学的计算化学
- 物理化学 物理化学
背景情况:
- 在自然和人工自组装系统中,π-π堆叠相互作用至关重要.
- 之前的研究量化了多环芳 (PAHs) 的相互作用.
- 含有异原子的芳香化合物 (HAC) 的分子间相互作用仍未得到充分研究.
研究的目的:
- 为了评估HACs在石墨表面上的相互作用能量 (Eint) 和稳定性与水平移位 (ΔEint) 相对应.
- 为了比较HACs与PAHs和n-alkanes的堆叠行为.
- 了解异质原子在 π-π 堆叠相互作用中的作用.
主要方法:
- 密度函数理论 (DFT) 计算与分散校正.
- 使用C96H24.24建模石墨表面.
- 计算Eint和ΔEint对于各种HACs (thiophene, pyridine, furan, pyrrole) 的计算.
主要成果:
- 烯和二烯的相互作用能量与二烯相当.
- furan 和 pyrrole 的相互作用能量低于的相互作用能量.
- 相互作用能量与重原子的数量线性增加,类似于PAHs.
- 分散力是主要的吸引力相互作用.
结论:
- 与PAH相比,异原子不会显著改变相互作用能量或堆叠稳定性.
- 在与石墨堆叠相互作用方面,HACs可以与PAHs相似地处理.
- 分散力是HAC和石墨之间吸引力的关键驱动力.
相关概念视频
Frost Circles for Different Conjugated Systems
4.0K
The inscribed polygon method is consistent with Hückel’s 4n + 2 rule and helps to learn whether the given cyclic compound is aromatic or not. The compound is stable and aromatic if every bonding molecular orbital (MO) is completely filled with a pair of electrons. However, if the non-bonding or antibonding orbitals are filled with electrons, the compound is unstable and not aromatic. Consider the Frost circle diagrams for cycloalkenes containing 4 to 8 carbons.
4.0K
Five-Membered Heterocyclic Aromatic Compounds: Overview
5.9K
Heterocyclic aromatic compounds are cyclic compounds that are aromatic and have one or more heteroatoms—atoms other than carbon, in the ring. Depending upon the number of atoms present in the ring, they can be either five or six-membered. Examples of five-membered heterocyclic aromatic compounds include pyrrole, furan, thiophene, and imidazole. Pyrrole consists of one nitrogen atom having one lone pair of electrons. Furan and thiophene have one oxygen and one sulfur heteroatom,...
5.9K
Stability of Substituted Cyclohexanes
16.5K
This lesson discusses the stability of substituted cyclohexanes with a focus on energies of various conformers and the effect of 1,3-diaxial interactions.
The two chair conformations of cyclohexanes undergo rapid interconversion at room temperature. Both forms have identical energies and stabilities, each comprising equal amounts of the equilibrium mixture. Replacing a hydrogen atom with a functional group makes the two conformations energetically non-equivalent.
For example, in...
The two chair conformations of cyclohexanes undergo rapid interconversion at room temperature. Both forms have identical energies and stabilities, each comprising equal amounts of the equilibrium mixture. Replacing a hydrogen atom with a functional group makes the two conformations energetically non-equivalent.
For example, in...
16.5K
π Electron Effects on Chemical Shift: Aromatic and Antiaromatic Compounds
2.0K
In aromatic compounds, such as benzene, the circulation of (4n + 2) π-electrons sets up a diamagnetic or diatropic ring current around the perimeter of the molecule. This current induces a magnetic field that opposes the external field inside the ring and reinforces it on the outside. The protons in benzene are deshielded and exhibit high chemical shifts in the range 6.5–8.5 ppm. The shielding effect at the center of the ring is evident in complex aromatic molecules, such as...
2.0K
Combustion Energy: A Measure of Stability in Alkanes and Cycloalkanes
8.1K
The low reactivity in alkanes can be attributed to the non-polar nature of C–C and C–H σ bonds. Alkanes, therefore, were initially termed as “paraffins,” derived from the Latin words: parum, meaning “too little,” and affinis, meaning “affinity.”
Alkanes undergo combustion in the presence of excess oxygen and high-temperature conditions to give carbon dioxide and water. A combustion reaction is the energy source in natural gas, liquified...
Alkanes undergo combustion in the presence of excess oxygen and high-temperature conditions to give carbon dioxide and water. A combustion reaction is the energy source in natural gas, liquified...
8.1K
Criteria for Aromaticity and the Hückel 4n + 2 Rule
14.3K
Like benzene, cyclobutadiene and cyclooctatetraene are cyclic compounds with alternate single and double bonds. However, their chemical behavior differs from benzene, as they are unstable and not aromatic. So, what are the structural characteristics of unsaturated compounds categorized as aromatic?
For the first time, Eric Hückel, a German chemical physicist, derived a set of structural features for a compound to be classified as aromatic. This is now known as Hückel’s rule or the 4n +...
For the first time, Eric Hückel, a German chemical physicist, derived a set of structural features for a compound to be classified as aromatic. This is now known as Hückel’s rule or the 4n +...
14.3K


