Localized hybrid exchange-correlation Potentials for Kohn-Sham DFT calculations of NMR and EPR parameters

被引:28
作者
Arbuznikov, AV [1 ]
Kaupp, M [1 ]
机构
[1] Univ Wurzburg, Inst Organ Chem, D-97074 Wurzburg, Germany
关键词
density functional theory; hybrid functionals; localized hybrid potentials; Kohn-Sham potential; optimized effective potential; localized Hartree-Fock method; nuclear shielding constants; electronic g-tensors;
D O I
10.1002/qua.20513
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
in contrast to the conventional, nonlocal, and nonmultiplicative implementation of hybrid exchange-correlation functionals in self-consistent calculations, the exact-exchange contribution to the functional has been implemented as a proper local and multiplicative Kohn-Sham potential, using the localized Hartree-Fock approximation to the optimized effective potential. The resulting localized hybrid potentials provide improved performance over nonlocal implementations in density functional theory (DFT) calculations of nuclear shielding constants of main-group molecules and electronic g-tensors of 3d transition-metal complexes. Optimum performance of the localized potentials is found at very similar amounts of exact-exchange admixture for both properties and is almost independent of the "pure-DFT" exchange and correlation functionals combined with exact exchange. Based on local kinetic energy density, a measure of exact-exchange admixture is constructed that helps rationalize the relatively large optimal exact-exchange contributions found. (c) 2005 Wiley Periodicals, Inc.
引用
收藏
页码:261 / 271
页数:11
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