从轨道选择性外势计算研究立体化学活性孤对电子的微观机理
Microscopic Mechanism of Stereochemically Active Lone Pair Studied from Orbital Selective External Potential Calculation
摘要：
立体化学活性孤对电子的性质长期以来一直存在争议。本文应用我们最近发展的轨道选择性外势（OSEP）方法，研究了各种化合物中立体化学活性孤对电子的微观机理。OSEP方法允许我们移动特定原子轨道的能级，因此有助于明确地确定该轨道对我们感兴趣的体系的化学和物理性质的作用。我们的数值计算结果，令人信服的证据表明，现场混合的阳离子价的s轨道与名义上空的p轨道的同一子壳层是至关重要的孤对形成，而阴离子的p轨道只有很小的影响。我们对Sn和Pb单硫族化合物的详细研究表明，这些系统的结构对孤对电子有显著的影响。反过来，孤对电子的形成，这可以通过我们的OSEP方法控制，可能会导致Sn和Pb单硫族化合物的结构不稳定性。
英文摘要：
The nature of the stereochemically active lone pair has long been in debate. Here, by application of our recently developed orbital selective external potential (OSEP) method, we have studied the microscopic mechanism of stereochemically active lone pairs in various compounds. The OSEP method allows us to shift the energy level of specific atomic orbital, therefore is helpful to identify unambiguously the role of this orbital to the chemical and physical properties of the system we are interested in. Our numerical results, with compelling proofs, demonstrate that the on-site mixing of cation valence s orbital with the nominally empty p orbitals of the same subshell is crucial to the formation of lone pair, whereas the anion p orbital has only small effect. Our detailed investigation of Sn and Pb monochalcogenides show that structures of these systems have significant effects on lone pairs. In return, the formation of lone pair, which can be controlled by our OSEP method, could result in structural instabilities of Sn and Pb monochalcogenides.
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