相关实验视频
Updated: May 9, 2026

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Original Experimental Approach for Assessing Transport Fuel Stability
Published on: October 21, 2016
对基的相对稳定性的相关关系效应
William C McKee1, Paul von Ragué Schleyer
1Center for Computational Chemistry and Department of Chemistry, University of Georgia, Athens, Georgia 30602, United States.
Journal of the American Chemical Society
|August 6, 2013
概括
高分支的基和具有"原分支"的基由于电子关联效应而更稳定. 这些效应,特别是在1,3-基组之间,增强了基稳定性和相关性能量.
科学领域:
- 计算化学的计算化学
- 有机化学 有机化学
- 物理化学 物理化学
背景情况:
- 阿尔干分支效应描述了与它们的线性异构体 (例如,n-butan) 相比,分支的阿尔干 (例如,异布) 的稳定性增加.
- 线性基呈现出线性基的表现.
- 原分支的原始分支
- 它们是1,3-基-基相互作用,有助于降低能量.
研究的目的:
- 为了研究分支和原分支基的稳定能量的起源.
- 阐明电子相关性在稳定中的作用.
主要方法:
- 对原分支的基与乙进行异体比较.
- 精确的初始计算使用后自相一致的场处理 (SCF).
- 局部化分子轨道第二阶的Møller-Plesset (LMO-MP2) 对应能量的分割.
主要成果:
- 分支和原分支导致中显著的稳定能.
- 中距离电子相关性 (1.5-3.0 Å) 对于准确描述稳定性至关重要.
- LMO-MP2分析显示,1,3-基组之间的电子相关性是增强稳定性的主要驱动因素.
结论:
- 电子关联效应,特别是在1,3-基相互作用中,对分支和原分支基的增强稳定性负责.
- 需要精确的量子化学方法来捕捉这些微妙的稳定效应.
相关概念视频
Relative Stabilities of Alkenes
The relative stability of alkenes can be determined by comparing their heats of hydrogenation. The lower heat of hydrogenation indicates the more stable alkene. The three main factors determining the relative stability of alkenes are i) the number of substituents attached to the double-bond carbon atoms, ii) hyperconjugation, and iii) the stereochemistry of the double bond.
Combustion Energy: A Measure of Stability in Alkanes and Cycloalkanes
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 petroleum gas (LPG), fuel oil, gasoline, diesel fuel, and...
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 petroleum gas (LPG), fuel oil, gasoline, diesel fuel, and...
Physical Properties of Alkanes
Alkanes are nonpolar molecules due to the presence of only carbon and hydrogen atoms. The electronegativity difference between carbon and hydrogen is minimal, and hence alkanes have a zero dipole moment. This leads to the presence of only dispersion forces between the molecules. The strength of dispersion forces is dependent on the surface area of the molecules on which they act. Since the surface area increases with the molecular length for straight-chain alkanes, the dispersion forces also...
Acidity of 1-Alkynes
The acidic strength of hydrocarbons follows the order: Alkynes > Alkenes > Alkanes. The strength of an acid is commonly expressed in units of pKa — the lower the pKa, the stronger the acid. Among the hydrocarbons, terminal alkynes have lower pKa values and are, therefore, more acidic. For example, the pKa values for ethane, ethene, and acetylene are 51, 44, and 25, respectively, as shown here.
Structure and Bonding of Alkenes
Olefins, which are unsaturated hydrocarbons containing one or more carbon–carbon double bonds, are broadly divided into alkenes and cycloalkenes. The general chemical formula of an alkene is CnH2n.
Doubly bonded carbons are sp2 hybridized and have a trigonal planar geometry. The double bond is composed of a σ bond formed by the overlap of hybrid orbitals and a π bond produced by the lateral overlap of unhybridized 2p orbitals on both the carbons. Each carbon atom is bonded to two hydrogen atoms...
Doubly bonded carbons are sp2 hybridized and have a trigonal planar geometry. The double bond is composed of a σ bond formed by the overlap of hybrid orbitals and a π bond produced by the lateral overlap of unhybridized 2p orbitals on both the carbons. Each carbon atom is bonded to two hydrogen atoms...
Constitutional Isomers of Alkanes
Organic compounds of the same molecular formula can have different structural formulas called constitutional isomers, and the phenomenon is known as constitutional isomerism. Alkanes with four or more carbons showing multiple structures with the same molecular formula thereby exhibit constitutional isomerism.
The linear isomer of an alkane is prefixed by the term “n”; hence a linear isomer of pentane is known as n-pentane. Based on the type of branching, some of the branched isomers are given...
The linear isomer of an alkane is prefixed by the term “n”; hence a linear isomer of pentane is known as n-pentane. Based on the type of branching, some of the branched isomers are given...

