Four-component relativistic theory for nuclear magnetic shielding: Magnetically balanced gauge-including atomic orbitals
文献类型：期刊论文
| 作者 | Cheng, Lan; Xiao, Yunlong; Liu, Wenjian1 |
| 刊名 | JOURNAL OF CHEMICAL PHYSICS
 |
| 出版日期 | 2009-12-28 |
| 卷号 | 131期号:24 |
| 关键词 | Dirac Equation Electron Correlations Magnetic Shielding Molecular Electronic States Nuclear Magnetic Resonance Orbital Calculations Paramagnetism Relativistic Corrections |
| ISSN号 | 0021-9606 |
| 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. |
| 语种 | 英语 |
| WOS记录号 | WOS:000273217000018 |
| 出版者 | AMER INST PHYSICS |
| 源URL | [http://ir.iccas.ac.cn/handle/121111/67549]  |
| 专题 | 中国科学院化学研究所 |
| 通讯作者 | Liu, Wenjian |
| 作者单位 | 1.Peking Univ, Coll Chem & Mol Engn, Inst Theoret & Computat Chem, Beijing Natl Lab Mol Sci,State Key Lab Rare Earth, Beijing 100871, Peoples R China 2.Peking Univ, Ctr Computat Sci & Engn, Beijing 100871, Peoples R China |
| 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,2009,131(24). |
| 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,131(24). |
| MLA | Cheng, Lan,et al."Four-component relativistic theory for nuclear magnetic shielding: Magnetically balanced gauge-including atomic orbitals".JOURNAL OF CHEMICAL PHYSICS 131.24(2009). |
入库方式： OAI收割
来源：化学研究所
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