Effects of Spin鈥揙rbit Coupling on Covalent Bonding and the Jahn鈥揟eller Effect Are Revealed with the Natural Language of Spinors

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• 作者：Tao Zeng ; Dmitri G. Fedorov ; Michael W. Schmidt ; Mariusz Klobukowski
• 刊名：Journal of Chemical Theory and Computation
• 出版年：2011
• 出版时间：September 13, 2011
• 年：2011
• 卷：7
• 期：9
• 页码：2864-2875
• 全文大小：1005K
• 年卷期：v.7,no.9(September 13, 2011)
• ISSN：1549-9626

文摘

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鈥搊rbit natural spinors (Zeng, T. et al. J. Chem. Phys. 2011, 134, 214107). This novel method gives chemical insights into the role of spin鈥搊rbit coupling in covalent bonding and in the Jahn鈥揟eller effect. The natural spinors are used to explain antibonding spin鈥搊rbit effects on TlH and Tl₂: it is found that the spin鈥搊rbit 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鈥搊rbit quenching of the Jahn鈥揟eller effect in WF₅: the spin鈥搊rbit 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鈥搊rbit coupling in covalent bonding and Jahn鈥揟eller effect is given in terms of the competition between the rotational nature of the spin鈥搊rbit 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.