Strong electron correlation in UO2-: A photoelectron spectroscopy and relativistic quantum chemistry study
文献类型：期刊论文
| 作者 | Li, WL ; Su, J ; Jian, T ; Lopez, GV ; Hu, HS ; Cao, GJ ; Li, J ; Wang, LS |
| 刊名 | JOURNAL OF CHEMICAL PHYSICS
 |
| 出版日期 | 2014 |
| 卷号 | 140期号:9 |
| 关键词 | BASIS-SETS INFRARED-SPECTRA ACTINYL IONS GAS-PHASE PERTURBATION-THEORY SPIN-ORBIT MOLECULES ATOMS COMPLEXES ELEMENTS |
| ISSN号 | 0021-9606 |
| 通讯作者 | junli@tsinghua.edu.cn ; lai-sheng_wang@brown.edu |
| 英文摘要 | The electronic structures of actinide systems are extremely complicated and pose considerable challenges both experimentally and theoretically because of significant electron correlation and relativistic effects. Here we report an investigation of the electronic structure and chemical bonding of uranium dioxides, UO2- and UO2, using photoelectron spectroscopy and relativistic quantum chemistry. The electron affinity of UO2 is measured to be 1.159(20) eV. Intense detachment bands are observed from the UO2- low-lying (7s sigma(g))(2)(5f phi(u))(1) orbitals and the more deeply bound O2p-based molecular orbitals which are separated by a large energy gap from the U-based orbitals. Surprisingly, numerous weak photodetachment transitions are observed in the gap region due to extensive two-electron transitions, suggesting strong electron correlations among the (7s sigma(g))(2)(5f phi(u))(1) electrons in UO2- and the (7s sigma(g))(1)(5f phi(u))(1) electrons in UO2. These observations are interpreted using multi-reference ab initio calculations with inclusion of spin-orbit coupling. The strong electron correlations and spin-orbit couplings generate orders-of-magnitude more detachment transitions from UO2- than expected on the basis of the Koopmans' theorem. The current experimental data on UO2- provide a long-sought opportunity to arbitrating various relativistic quantum chemistry methods aimed at handling systems with strong electron correlations. (C) 2014 AIP Publishing LLC. |
| 收录类别 | SCI |
| 语种 | 英语 |
| WOS记录号 | WOS:000334067400018 |
| 公开日期 | 2015-03-13 |
| 源URL | [http://ir.sinap.ac.cn/handle/331007/14414]  |
| 专题 | 上海应用物理研究所_中科院上海应用物理研究所2011-2017年 |
| 推荐引用方式 GB/T 7714 | Li, WL,Su, J,Jian, T,et al. Strong electron correlation in UO2-: A photoelectron spectroscopy and relativistic quantum chemistry study[J]. JOURNAL OF CHEMICAL PHYSICS,2014,140(9). |
| APA | Li, WL.,Su, J.,Jian, T.,Lopez, GV.,Hu, HS.,...&Wang, LS.(2014).Strong electron correlation in UO2-: A photoelectron spectroscopy and relativistic quantum chemistry study.JOURNAL OF CHEMICAL PHYSICS,140(9). |
| MLA | Li, WL,et al."Strong electron correlation in UO2-: A photoelectron spectroscopy and relativistic quantum chemistry study".JOURNAL OF CHEMICAL PHYSICS 140.9(2014). |
入库方式： OAI收割
来源：上海应用物理研究所
浏览0
下载0
收藏0
其他版本
除非特别说明，本系统中所有内容都受版权保护，并保留所有权利。