Ab Initio Study on Mixed Inorganic/Organic Ligand Sandwich Clusters: BzTMC60, TM = Sc−Co

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• 作者：Liyan Zhu ; Tingting Zhang ; Mengxi Yi ; Jinlan Wang
• 刊名：Journal of Physical Chemistry A
• 出版年：2010
• 出版时间：September 2, 2010
• 年：2010
• 卷：114
• 期：34
• 页码：9398-9403
• 全文大小：424K
• 年卷期：v.114,no.34(September 2, 2010)
• ISSN：1520-5215

文摘

We have systematically investigated mixed inorganic/organic ligand sandwich clusters comprised of 3d transition metal (TM) atoms with C₆₀ and benzene (Bz) molecules, BzTMC₆₀, by using all electron density functional theory. We found the bonding type between TM and C₆₀ in the ground state evolves from η⁶ (TM = Sc−Cr) to η⁵ (TM = Mn) and then to η² (TM = Fe, Co) with increasing number of d electrons of TM. The BzTMC₆₀ clusters (TM = Sc−Co) are of high stability through ionic−covalent interactions. The BzCrC₆₀ cluster has the lowest binding energy due to its largest spin-flip energy and the weakest ionic bonding interaction between the CrBz unit and C₆₀. With the exception of BzTiC₆₀ being triplet, all the BzTMC₆₀ clusters energetically prefer the lowest available spin states, e.g., the ground spin state is either a singlet (with an even number of electrons) or a doublet (with an odd number of electrons). Moreover, the magnetic properties of BzTMC₆₀ show clear dependence to the bond type between TM and C₆₀, and the η⁵-ligand configurations tend to be in high spin states.