Zeng Tao, Fedorov Dmitri G, Schmidt Michael W, Klobukowski Mariusz
Department of Chemistry, University of Alberta , Edmonton, Alberta, Canada, T6G 2G2.
NRI, National Institute of Advanced Industrial Science and Technology (AIST), Central 2, Umezono 1-1-1, Tsukuba, 305-8568, Japan.
J Chem Theory Comput. 2011 Sep 13;7(9):2864-75. doi: 10.1021/ct200457q. Epub 2011 Aug 29.
The orbital-based natural language describing the complexity of chemistry ( Stowasser , R. ; Hoffmann , R. J. Am. Chem. Soc. 1999 , 121 , 3414 ) was extended by us recently to the definition of spin-orbit natural spinors ( Zeng , T. et al. J. Chem. Phys. 2011 , 134 , 214107 ). This novel method gives chemical insights into the role of spin-orbit coupling in covalent bonding and in the Jahn-Teller effect. The natural spinors are used to explain antibonding spin-orbit effects on TlH and Tl2: it is found that the spin-orbit induced charge transfer from the bonding to the nonbonding or antibonding orbitals has a large effect on the bond strength. The natural spinors are also used to explain the spin-orbit quenching of the Jahn-Teller effect in WF5: the spin-orbit interaction can stabilize the totally symmetric electron distribution so that the high-symmetry molecular structure becomes more stable than its distortions. A general discussion of the role of the spin-orbit coupling in covalent bonding and Jahn-Teller effect is given in terms of the competition between the rotational nature of the spin-orbit coupling and the directionality of the two effects. The natural spinors offer the advantage of providing a simple and clear pictorial explanation for the profound relativistic spin-dependent interactions in chemistry often appearing as a black box answer.
基于轨道的描述化学复杂性的自然语言（斯托瓦塞尔，R.；霍夫曼，R.《美国化学会志》1999年，121卷，3414页）最近被我们扩展到了自旋轨道自然旋量的定义（曾，T.等人《化学物理杂志》2011年，134卷，214107页）。这种新方法为自旋轨道耦合在共价键和 Jahn - Teller 效应中的作用提供了化学见解。自然旋量被用于解释对 TlH 和 Tl₂ 的反键自旋轨道效应：发现自旋轨道诱导的电荷从成键轨道转移到非键或反键轨道对键强度有很大影响。自然旋量还被用于解释 WF₅ 中 Jahn - Teller 效应的自旋轨道猝灭：自旋轨道相互作用可以稳定完全对称的电子分布，使得高对称分子结构比其畸变结构更稳定。从自旋轨道耦合的旋转性质与这两种效应的方向性之间的竞争角度，对自旋轨道耦合在共价键和 Jahn - Teller 效应中的作用进行了一般性讨论。自然旋量提供了一个优势，即能为化学中常常看似是一个黑箱答案的深刻相对论自旋相关相互作用提供简单明了的图像解释。
