Wang, JQ
; Zhang, S (reprint author), Chinese Acad Sci, Shanghai Inst Appl Phys, Shanghai 201204, Peoples R China.
文章类型:
期刊文献
英文摘要:
To shed some light on the metal 3d ground state configuration of cobalt phthalocyanines system, so far in debate, we present an investigation by X-ray absorption spectroscopy (XAS) at Co L-2,(3) edge and theoretical calculation. The density functional theory calculations reveal highly anisotropic covalent bond between central cobalt ion and nitrogen ligands, with the dominant sigma donor accompanied by weak pi-back acceptor interaction. Our combined experimental and theoretical study on the Co-L-2,L-3 XAS spectra demonstrate a robust ground state of (2)A(1g) symmetry that is built from 73% 3d(7) character and 27% 3d(8)L (L denotes a ligand hole) components, as the first excited-state with E-2(g) symmetry lies about 158 meV higher in energy. The effect of anisotropic and isotropic covalency on the ground state was also calculated and the results indicate that the ground state with (2)A(1g) symmetry is robust in a large range of anisotropic covalent strength while a transition of ground state from (2)A(1g) to E-2(g) configuration when isotropic covalent strength increases to a certain extent. Here, we address a significant anisotropic covalent effect of short Co(II)-N bond on the ground state and suggest that it should be taken into account in determining the ground state of analogous cobalt complexes. (c) 2016 Author(s).
Zhou, J,Zhang, LJ,Hu, ZW,et al. The significant role of covalency in determining the ground state of cobalt phthalocyanines molecule[J]. AIP ADVANCES,2016-01-01,6(3):—.
