Theoretical studies of the local structures and EPR parameters for various Rh2+ centers in AgCl

doi:10.1016/j.theochem.2010.05.021

IMR OpenIR

	Theoretical studies of the local structures and EPR parameters for various Rh2+ centers in AgCl
	Zhang, Hua-Ming 1; Wu, Shao-Yi 1,2; Xu, Pei 1; Li, Li-Li 1
通讯作者	Wu, Shao-Yi(wushaoyi@netease.com)
	2010-08-15
发表期刊	JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM
ISSN	0166-1280
卷号	953 期号:1-3 页码:157-162
摘要	The local structures and electron paramagnetic resonance (EPR) parameters (the g factors, the hyperfine structure constants and the superhyperfine parameters) for various Rh2+ centers in AgCl are theoretically studied using the perturbation formulas of these parameters for a 4d(7) ion in tetragonally and orthorhombically distorted octahedra. These defects include the tetragonally and orthorhombically elongated centers at low temperatures (labeled as T-L and O-L) and the tetragonally compressed center at high temperature (labeled as T-H). The centers T-L and O-L are attributed to the substitutional Rh2+ on Ag+ site, associated with none and one next nearest neighbour cation vacancy V-Ag along [1 0 0] (or X) axis, respectively. The ligand octahedron in the orthorhombic center O-L is found to suffer the relative elongation Delta Z(OL) approximate to 0.079 angstrom along [0 01] (or Z) axis due to the Jahn-Teller effect, and the intervening ligand Cl- in the V-Ag and the Rh2+ may experience the inward displacement Delta X approximate to 0.008 angstrom towards the central Rh2*. In the center T-L, the uncompensated [RhCl6](4-) cluster is found to suffer the relative elongation Delta Z(TL) approximate to 0.116 angstrom along [0 0 1] axis due to the Jahn-Teller effect. As for the center T-H, one V-Ag occurs in the next nearest neighbour site along [0 0 1] axis, which may compel the intervening Cl- in the V-Ag and the Rh2+ to shift towards the central Rh2+ by an amount Delta Z(H) approximate to 0.112 angstrom. In the calculations of the superhyperfine parameters, the related molecular orbital coefficients and the ligand unpaired spin densities are determined quantitatively from the cluster approach in a uniform way. The theoretical EPR parameters based on the above local structures show good agreement with the experimental data for all the centers. (C) 2010 Elsevier B.V. All rights reserved.
关键词	Crystal-fields and spin Hamiltonians Electron paramagnetic resonance (EPR) Rh2+ AgCl
资助者	Support Program for Academic Excellence of UESTC
DOI	10.1016/j.theochem.2010.05.021
收录类别	SCI
语种	英语
资助项目	Support Program for Academic Excellence of UESTC
WOS研究方向	Chemistry
WOS类目	Chemistry, Physical
WOS记录号	WOS:000280119000021
出版者	ELSEVIER SCIENCE BV
引用统计	被引频次：15[WOS] [WOS记录] [WOS相关记录]
文献类型	期刊论文
条目标识符	http://ir.imr.ac.cn/handle/321006/103262
专题	中国科学院金属研究所
通讯作者	Wu, Shao-Yi
作者单位	1.Univ Elect Sci & Technol China, Inst Appl Phys, Chengdu 610054, Peoples R China 2.Chinese Acad Sci, Int Ctr Mat Phys, Shenyang 110016, Peoples R China
推荐引用方式 GB/T 7714	Zhang, Hua-Ming,Wu, Shao-Yi,Xu, Pei,et al. Theoretical studies of the local structures and EPR parameters for various Rh2+ centers in AgCl[J]. JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM,2010,953(1-3):157-162.
APA	Zhang, Hua-Ming,Wu, Shao-Yi,Xu, Pei,&Li, Li-Li.(2010).Theoretical studies of the local structures and EPR parameters for various Rh2+ centers in AgCl.JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM,953(1-3),157-162.
MLA	Zhang, Hua-Ming,et al."Theoretical studies of the local structures and EPR parameters for various Rh2+ centers in AgCl".JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM 953.1-3(2010):157-162.