Four-component relativistic theory for nuclear magnetic shielding:   Magnetically balanced gauge-including atomic orbitals

doi:10.1063/1.3283036

CORC > 北京大学 > 化学与分子工程学院

	Four-component relativistic theory for nuclear magnetic shielding: Magnetically balanced gauge-including atomic orbitals
	Cheng, Lan ; Xiao, Yunlong ; Liu, Wenjian
刊名	journal of chemical physics
	2009
关键词	Dirac equation electron correlations magnetic shielding molecular electronic states nuclear magnetic resonance orbital calculations paramagnetism relativistic corrections NMR CHEMICAL-SHIFTS DIRAC-FOCK CALCULATIONS SPIN COUPLING TENSORS HYDROGEN HALIDES CONFIGURATION-INTERACTION LOCALIZED QUANTITIES PROGRAM PACKAGE EXCHANGE-ENERGY WAVE-FUNCTIONS SUSCEPTIBILITIES
DOI	10.1063/1.3283036
英文摘要	It is recognized only recently that the incorporation of the magnetic balance condition is absolutely essential for four-component relativistic theories of magnetic properties. Another important issue to be handled is the so-called gauge problem in calculations of, e.g., molecular magnetic shielding tensors with finite bases. It is shown here that the magnetic balance can be adapted to distributed gauge origins, leading to, e.g., magnetically balanced gauge-including atomic orbitals (MB-GIAOs) in which each magnetically balanced atomic orbital has its own local gauge origin placed on its center. Such a MB-GIAO scheme can be combined with any level of theory for electron correlation. The first implementation is done here at the coupled-perturbed Dirac-Kohn-Sham level. The calculated molecular magnetic shielding tensors are not only independent of the choice of gauge origin but also converge rapidly to the basis set limit. Close inspections reveal that (zeroth order) negative energy states are only important for the expansion of first order electronic core orbitals. Their contributions to the paramagnetism are therefore transferable from atoms to molecule and are essentially canceled out for chemical shifts. This allows for simplifications of the coupled-perturbed equations.; http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000273217000018&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=8e1609b174ce4e31116a60747a720701 ; Physics, Atomic, Molecular & Chemical; SCI(E); EI; 40; ARTICLE; 24; 131
语种	英语
内容类型	期刊论文
源URL	[http://ir.pku.edu.cn/handle/20.500.11897/244933]
专题	化学与分子工程学院
推荐引用方式 GB/T 7714	Cheng, Lan,Xiao, Yunlong,Liu, Wenjian. Four-component relativistic theory for nuclear magnetic shielding: Magnetically balanced gauge-including atomic orbitals[J]. journal of chemical physics,2009.
APA	Cheng, Lan,Xiao, Yunlong,&Liu, Wenjian.(2009).Four-component relativistic theory for nuclear magnetic shielding: Magnetically balanced gauge-including atomic orbitals.journal of chemical physics.
MLA	Cheng, Lan,et al."Four-component relativistic theory for nuclear magnetic shielding: Magnetically balanced gauge-including atomic orbitals".journal of chemical physics (2009).