Understanding the Magnetic Anisotropy in a Family of N-2(3-)   Radical-Bridged Lanthanide Complexes: Density Functional Theory and ab   Initio Calculations

doi:10.1021/jp4044495

CORC > 北京大学 > 化学与分子工程学院

	Understanding the Magnetic Anisotropy in a Family of N-2(3-) Radical-Bridged Lanthanide Complexes: Density Functional Theory and ab Initio Calculations
	Zhang, Yi-Quan ; Luo, Cheng-Lin ; Wang, Bing-Wu ; Gao, Song
刊名	journal of physical chemistry a
	2013
关键词	SINGLE-MOLECULE MAGNET EXCHANGE COUPLING-CONSTANTS GAUSSIAN-BASIS SETS ATOMS LI BEHAVIOR BARRIER SYSTEMS KR
DOI	10.1021/jp4044495
英文摘要	Density functional theory (DFT) and ab initio methods were used to investigate the influence of both intramolecular exchange coupling and single-ion anisotropy on the relaxation barriers of a series of N-2(3-) radical-bridged lanthanide complexes [{[(Me3Si)(2)N](2)(THF)Ln}(2)(mu-eta(2):eta(2)-N-2)](-) (Ln = Gd-III (1), Tb-III (2), Dy-III (3), Ho-III (4), and Er-III (5)) reported by Long and co-workers. DFT calculations show that the exchange coupling between the lanthanide ions is very weak, but the Ln-N-2(3-) coupling is strong for each complex. Moreover, the exchange couplings of Ln-N-2(3-) are antiferromagnetic for Ln = Gd-III, Tb-III, Dy-III, and Ho-III but ferromagnetic for Er-III for the nearly orthogonal magnetic orbitals on Er-III and N-2(3-). Ab initio calculations show that both of the large magnetic anisotropy of single Tb fragment and the strong Tb-N-2(3-) antiferromagnetic couplings lead to the largest energy barrier of complex 2. Although the energy barrier of a single Er fragment is the second largest, the relaxation barrier of complex 5 is only 36.0 cm(-1) due to the weak Er-III-N-2(3-) coupling. This study suggests that both intramolecular exchange coupling and single-ion anisotropy contribute greatly to the full relaxation barrier of lanthanide-based single-molecule magnets (SMMs), which expands the understanding of SMMs using only the giant-spin model.; http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000326259700007&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=8e1609b174ce4e31116a60747a720701 ; Chemistry, Physical; Physics, Atomic, Molecular & Chemical; SCI(E); EI; PubMed; 10; ARTICLE; 42; 10873-10880; 117
语种	英语
内容类型	期刊论文
源URL	[http://ir.pku.edu.cn/handle/20.500.11897/149738]
专题	化学与分子工程学院
推荐引用方式 GB/T 7714	Zhang, Yi-Quan,Luo, Cheng-Lin,Wang, Bing-Wu,et al. Understanding the Magnetic Anisotropy in a Family of N-2(3-) Radical-Bridged Lanthanide Complexes: Density Functional Theory and ab Initio Calculations[J]. journal of physical chemistry a,2013.
APA	Zhang, Yi-Quan,Luo, Cheng-Lin,Wang, Bing-Wu,&Gao, Song.(2013).Understanding the Magnetic Anisotropy in a Family of N-2(3-) Radical-Bridged Lanthanide Complexes: Density Functional Theory and ab Initio Calculations.journal of physical chemistry a.
MLA	Zhang, Yi-Quan,et al."Understanding the Magnetic Anisotropy in a Family of N-2(3-) Radical-Bridged Lanthanide Complexes: Density Functional Theory and ab Initio Calculations".journal of physical chemistry a (2013).