3d-4f Magnetic Interaction with Density Functional Theory Plus U   Approach: Local Coulomb Correlation and Exchange Pathways

doi:10.1021/jp4103228

CORC > 北京大学 > 化学与分子工程学院

	3d-4f Magnetic Interaction with Density Functional Theory Plus U Approach: Local Coulomb Correlation and Exchange Pathways
	Zhang, Yachao ; Yang, Yang ; Jiang, Hong
刊名	journal of physical chemistry a
	2013
关键词	TRANSITION-METAL-COMPLEXES TOTAL-ENERGY CALCULATIONS SINGLE-MOLECULE-MAGNET AB-INITIO CALCULATIONS AUGMENTED-WAVE METHOD COUPLING-CONSTANTS ELECTRONIC-STRUCTURE LDA+U METHOD PBE0 MODEL HUBBARD-U
DOI	10.1021/jp4103228
英文摘要	The 3d-4f exchange interaction plays an important role in many lanthanide based molecular magnetic materials such as single-molecule magnets and magnetic refrigerants. In this work, we study the 3d-4f magnetic exchange interactions in a series of Cu(II)-Gd(III) (3d(9)-4f(7)) dinuclear complexes based on the numerical atomic basis-norm-conserving pseudopotential method and density functional theory plus the Hubbard U correction approach (DFT+U). We obtain improved description of the 4f electrons by including the semicore 5s5p states in the valence part of the Gd-pseudopotential. The Hubbard U correction is employed to treat the strongly correlated Cu-3d and Gd-4f electrons, which significantly improve the agreement of the predicted exchange constants, J, with experiment, indicating the importance of accurate description of the local Coulomb correlation. The high efficiency of the DFT+U approach enables us to perform calculations with molecular crystals, which in general improve the agreement between theory and experiment, achieving a mean absolute error smaller than 2 cm(-1). In addition, through analyzing the physical effects of U, we identify two magnetic exchange pathways. One is ferromagnetic and involves an interaction between the Cu-3d, O-2p (bridge ligand), and the majority-spin Gd-5d orbitals. The other one is antiferromagnetic and involves Cu-3d, O-2p, and the empty minority-spin Gd-4f orbitals, which is suppressed by the planar Cu-O-O-Gd structure. This study demonstrates the accuracy of the DFT+U method for evaluating the 3d-4f exchange interactions, provides a better understanding of the exchange mechanism in the Cu(II)-Gd(III) complexes, and paves the way for exploiting the magnetic properties of the 3d-4f compounds containing lanthanides other than Gd.; http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000328529300017&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=8e1609b174ce4e31116a60747a720701 ; Chemistry, Physical; Physics, Atomic, Molecular & Chemical; SCI(E); EI; PubMed; 5; ARTICLE; 49; 13194-13204; 117
语种	英语
内容类型	期刊论文
源URL	[http://ir.pku.edu.cn/handle/20.500.11897/149728]
专题	化学与分子工程学院
推荐引用方式 GB/T 7714	Zhang, Yachao,Yang, Yang,Jiang, Hong. 3d-4f Magnetic Interaction with Density Functional Theory Plus U Approach: Local Coulomb Correlation and Exchange Pathways[J]. journal of physical chemistry a,2013.
APA	Zhang, Yachao,Yang, Yang,&Jiang, Hong.(2013).3d-4f Magnetic Interaction with Density Functional Theory Plus U Approach: Local Coulomb Correlation and Exchange Pathways.journal of physical chemistry a.
MLA	Zhang, Yachao,et al."3d-4f Magnetic Interaction with Density Functional Theory Plus U Approach: Local Coulomb Correlation and Exchange Pathways".journal of physical chemistry a (2013).