Exact two-component relativistic theory for NMR parameters: General formulation and pilot application

被引:47
作者
Sun, Qiming
Xiao, Yunlong
Liu, Wenjian [1 ]
机构
[1] Peking Univ, State Key Lab Rare Earth Mat Chem & Applicat, Inst Theoret & Computat Chem, Beijing Natl Lab Mol Sci,Coll Chem & Mol Engn, Beijing 100871, Peoples R China
基金
中国国家自然科学基金;
关键词
diamagnetism; magnetisation; nuclear magnetic resonance; paramagnetism; perturbation theory; relativistic corrections; NUCLEAR MAGNETIC SHIELDINGS; DENSITY-FUNCTIONAL CALCULATIONS; REGULAR APPROXIMATION; PROGRAM PACKAGE; BASIS-SETS; ORDER; ENERGY; HAMILTONIANS; CHEMISTRY; CONSTANTS;
D O I
10.1063/1.4764042
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The previously proposed exact two-component (X2C) relativistic theory of nuclear magnetic resonance (NMR) parameters [Q. Sun, W. Liu, Y. Xiao, and L. Cheng, J. Chem. Phys. 131, 081101 (2009)] is reformulated to accommodate two schemes for kinetic balance, five schemes for magnetic balance, and three schemes for decoupling in a unified manner, at both matrix and operator levels. In addition, three definitions of spin magnetization are considered in the coupled-perturbed Kohn-Sham equation. Apart from its simplicity, the most salient feature of X2C-NMR lies in that its diamagnetic and paramagnetic terms agree individually with the corresponding four-component counterparts for any finite basis. For practical applications, five approximate schemes for the first order coupling matrix X-10 and four approximate schemes for the treatment of two-electron integrals are introduced, which render the computations of X2C-NMR very much the same as those of approximate two-component approaches. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4764042]
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页数:20
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