Probing the Structural, Bonding, and Magnetic Properties of Cobalt Coordination Complexes: Co鈥揃enzene, Co鈥揚yridine, and Co鈥揚yrimidine
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- 作者：Peng Shao ; Xiao-Yu Kuang ; Li-Ping Ding
- 刊名：Journal of Physical Chemistry A
- 出版年：2013
- 出版时间：December 5, 2013
- 年：2013
- 卷：117
- 期：48
- 页码：12998-13008
- 全文大小：786K
- 年卷期：v.117,no.48(December 5, 2013)
- ISSN：1520-5215
文摘
Neutral and anionic Co1,2(benzene)1,2, Co1,2(pyridine)1,2, and Co1,2(pyrimidine)1,2 complexes have been investigated within the framework of an all-electron gradient-corrected density functional theory. The ground-state structures for each size clusters were identified based on the geometry optimization. Meanwhile, their electron affinities and vertical detachment energies were predicted and compared with the experimental values. By analyzing the pattern of highest occupied molecular orbitals (HOMOs), we found that the bond formation of these Co鈥搊rganic complexes mainly arises from the 3d/4s electrons of the cobalt atoms and the 蟺-cloud of the organic molecules. More importantly, we presented an approach to map and analyze the Co鈥搊rganic interactions from another perspective. The scatter plots of the reduced density gradient (RDG) versus 蟻 allow us to identify the different types of interactions, and the maps of the gradient isosurfaces show a rich visualization of chemical bond and steric effects. Their magnetic properties were studied by determining the spin magnetic moments and visualizing the spin density distributions. Finally, the natural population analysis (NPA) charge was calculated to achieve a deep insight into the distribution of electron density and the reliable charge-transfer information.