期刊
JOURNAL OF PHYSICAL CHEMISTRY A
卷 114, 期 26, 页码 7179-7186出版社
AMER CHEMICAL SOC
DOI: 10.1021/jp102465x
关键词
-
资金
- EPSRC
- Norwegian Research Council [171185/V30, 197446/V30]
- CoE Centre for Theoretical and Computational Chemistry [179568/V30]
The influence of the optimized effective potential (OEP) and Coulomb-attenuation on shielding constants and chemical shifts is investigated for three disparate categories of molecule: main group, hydrogen bonded, and transition metal systems. Expanding the OEP in the orbital basis leads to physically sensible exchange-correlation potentials; OEP generalized gradient approximation results provide some indication of the accuracy of the expansion. OEP uncoupled magnetic parameters from representative hybrid and Coulomb-attenuated functionals can be a dramatic improvement over conventional results; both categories yield similar accuracy. Additional flexibility is introduced by expanding the OEP in an extensive even-tempered basis set, but this leads to the well-known problem of unphysical, oscillatory potentials. Smooth potentials are recovered through the use of a smoothing norm, but deficiencies in the procedure are highlighted for transition metal complexes. The study reiterates the importance of the OEP procedure in magnetic response calculations using orbital-dependent functionals, together with the need for careful attention to ensure physically sensible potentials. It also illustrates the utility of Coulomb-attenuated functionals for computing short-range molecular properties.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据