期刊
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
卷 9, 期 11, 页码 4789-4796出版社
AMER CHEMICAL SOC
DOI: 10.1021/ct4007184
关键词
-
资金
- Program of Emlpoyment of Newly Graduated Doctors of Science for Scientific Excellence [CZ.1.07/2.3.00/30.009]
- European Social Fund
- state budget of the Czech Republic
- European Regional Development Fund [CZ.1.05/1.1.00/02.0068]
- Czech Science Foundation [P206/12/0539]
- Norwegian Research Council through the CoE Centre for Theoretical and Computational Chemistry (CTCC) [179568/V30]
- Norwegian Supercomputing Program (NOTUR) [NN4654K]
- Department of Science and Technology, Govt. of India
- Research Council of University of Tehran
- National Grid Infrastructure Meta Centrum (Czech Republic) [LM2010005]
We present new insight into the nature of aromaticity in metal clusters. We give computational arguments in favor of using the ring-current model over local indices, such as nucleus independent chemical shifts, for the determination of the magnetic aromaticity. Two approaches for estimating magnetically induced ring currents are employed for this purpose, one based on the quantum theory of atoms in molecules (QTAIM) and the other where magnetically induced current densities (MICD) are explicitly calculated. We show that the two-zone aromaticity/antiaromaticity of a number of 3d metallic clusters (Sc-3(-), Cu-3(+), and Cu-4(2-)) can be explained using the QTAIM-based magnetizabilities. The reliability of the calculated atomic and bond magnetizabilities of the metallic clusters are verified by comparison with MICD computed at the multiconfiguration self-consistent field (MCSCF) and density functional levels of theory. Integrated MCSCF current strength susceptibilities as well as a visual analysis of the calculated current densities confirm the interpretations based on the QTAIM magnetizabilities. In view of the new findings, we suggest a simple explanation based on classical electromagnetic theory to explain the anomalous magnetic shielding in different transition metal clusters. Our results suggest that the nature of magnetic aromaticity/antiaromaticity in transition-metal clusters should be assessed more carefully based on global indices.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据