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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Nature of the Three-Electron Bond
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Nature of the Three-Electron Bond

机译：三电子键的性质

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摘要

We analyze the properties of 15 3-electron bonds, which include σ-3-electron-bonds, such as dihalide radical anions and di-noble gas radical cations, π-3-electron-bonds as in hydrazine radical cations, and doubly-π-(3e)-bonded species such as O_(2), FeO~(+), S_(2), etc. The primary analytical tool is the breathing-orbital valence-bond (BOVB) method, which enables us to quantify the charge shift resonance energy (RE_(CS)) of the three electrons, and the bond dissociation energies ( D _(e)). BOVB is tested reliable against MRCI calculations. Our findings show that in all 3-electron bonds, none of the VB structures have by themselves any bonding. In fact, in each VB structure, the three electrons maintain Pauli repulsion, while the entire bonding energy arises from resonance due to the charge shift between the two or more constituent VB structures. Hence, 3e-bonds are charge shift bonds (CSBs). The CSB character is probed by calculating the Laplacian ( L ) of the 3e-bond. Thus, much like the CSBs in electron-pair bonds, such as F_(2) or the central bond in [1.1.1]propellane, here too L is positive, thus showing the excess kinetic energy of the shared density due to the Pauli repulsion in the 3-electron VB structures. The RE_(CS) values for 3-electron bonds are invariably larger than the corresponding bond energies. For the doubly-π-(3e)-bonded species, RE_(CS) is very large, exceeding 100 kcal mol~(–1). As such, it is fitting to conclude that σ- and π-3-electron-bonds find their natural place in the CSB family along with two-electron CSBs, with which they share identical energetic and topological characteristics. Experimental manifestations/tests of 3e-CSBs are proposed.
机译：我们分析了15个3-电子键的性质，包括σ-3-电子键，例如二卤化物根部阴离子和二惰性气体阳离子，如肼自由基阳离子中的π-3-电子键，和双重 - π-（3E）诸如O_（2），FEO〜（+），S_（2）等的物种。主要分析工具是呼吸轨道价值 - 键（BOVB）方法，使我们能够量化三电子的电荷移位谐振能量（RE_（CS））和键解离子能量（D _（e））。 BOVB对MRCI计算可靠。我们的研究结果表明，在所有3个电子键中，VB结构都没有自己粘合。事实上，在每个VB结构中，三个电子保持Pauli排斥，而整个键合能源由于两个或更多个组成VB结构之间的电荷偏移而产生的谐振。因此，3E键是电荷换键（CSB）。通过计算3E键的Laplacian（L）来探测CSB字符。因此，与电子对键中的CSB一样，如F_（2）或[1.1.1]丙烷中的CSB，这里也是阳性的，因此显示由于保罗引起的共用密度的过度动能3-电子VB结构中的排斥。 3 - 电子键的RE_（CS）值总是大于相应的粘合能量。对于双π-（3E） - 粘合物种，RE_（CS）非常大，超过100kcal〜（-1）。因此，结论σ-和π-3 - 电子键在CSB系列中找到其自然位置以及两电子CSB，它们共享相同的能量和拓扑特征。提出了3E-CSB的实验表现/测试。

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