The significant role of covalency in determining the ground state of cobalt phthalocyanines molecule

doi:10.1063/1.4943773

CAS OpenIR > 中科院上海应用物理研究所2011-2018年

	The significant role of covalency in determining the ground state of cobalt phthalocyanines molecule
	Zhou, J; Zhang, LJ; Hu, ZW; Kuo, CY; Liu, HJ; Lin, X; Wang, Y; Pi, TW; Wang, JQ; Zhang, S; Zhang, S (reprint author), Chinese Acad Sci, Shanghai Inst Appl Phys, Shanghai 201204, Peoples R China.
	2016
发表期刊	AIP ADVANCES
ISSN	2158-3226
卷号	6 期号:3 页码:—
文章类型	期刊文献
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).
关键词	X-ray-absorption Electronic-structure Metal Phthalocyanines Edge Xas Spin Spectroscopy Porphyrin Co Corrole
DOI	10.1063/1.4943773
收录类别	SCI
语种	英语
WOS记录号	WOS:000373684200086
引用统计
文献类型	期刊论文
条目标识符	http://ir.sinap.ac.cn/handle/331007/25871
专题	中科院上海应用物理研究所2011-2018年
通讯作者	Wang, JQ; Zhang, S (reprint author), Chinese Acad Sci, Shanghai Inst Appl Phys, Shanghai 201204, Peoples R China.
推荐引用方式 GB/T 7714	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,2016,6(3):—.
APA	Zhou, J.,Zhang, LJ.,Hu, ZW.,Kuo, CY.,Liu, HJ.,...&Zhang, S .(2016).The significant role of covalency in determining the ground state of cobalt phthalocyanines molecule.AIP ADVANCES,6(3),—.
MLA	Zhou, J,et al."The significant role of covalency in determining the ground state of cobalt phthalocyanines molecule".AIP ADVANCES 6.3(2016):—.

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