Universität zu Köln

Zhou, Jing, Zhang, Linjuan, Hu, Zhiwei, Kuo, Changyang, Liu, Hengjie ORCID: 0000-0001-6499-3935, Lin, Xiao, Wang, Yu ORCID: 0000-0002-9071-0238, Pi, Tun-Wen, Wang, Jianqiang and Zhang, Shuo (2016). The significant role of covalency in determining the ground state of cobalt phthalocyanines molecule. AIP Adv., 6 (3). MELVILLE: AMER INST PHYSICS. ISSN 2158-3226

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Abstract

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).

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Zhou, Jing UNSPECIFIED UNSPECIFIED UNSPECIFIED Zhang, Linjuan UNSPECIFIED UNSPECIFIED UNSPECIFIED Hu, Zhiwei UNSPECIFIED UNSPECIFIED UNSPECIFIED Kuo, Changyang UNSPECIFIED UNSPECIFIED UNSPECIFIED Liu, Hengjie UNSPECIFIED orcid.org/0000-0001-6499-3935 UNSPECIFIED Lin, Xiao UNSPECIFIED UNSPECIFIED UNSPECIFIED Wang, Yu UNSPECIFIED orcid.org/0000-0002-9071-0238 UNSPECIFIED Pi, Tun-Wen UNSPECIFIED UNSPECIFIED UNSPECIFIED Wang, Jianqiang UNSPECIFIED UNSPECIFIED UNSPECIFIED Zhang, Shuo UNSPECIFIED UNSPECIFIED UNSPECIFIED
URN:	urn:nbn:de:hbz:38-282319
DOI:	10.1063/1.4943773
Journal or Publication Title:	AIP Adv.
Volume:	6
Number:	3
Date:	2016
Publisher:	AMER INST PHYSICS
Place of Publication:	MELVILLE
ISSN:	2158-3226
Language:	English
Faculty:	Unspecified
Divisions:	Unspecified
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language X-RAY-ABSORPTION; ELECTRONIC-STRUCTURE; EDGE XAS; SPIN; CO; CORROLE Multiple languages Nanoscience & Nanotechnology; Materials Science, Multidisciplinary; Physics, Applied Multiple languages
Refereed:	Yes
URI:	http://kups.ub.uni-koeln.de/id/eprint/28231