Infrared Spectroscopic and Theoretical Studies of the 3d Transition Metal Oxyfluoride Molecules
文献类型：期刊论文
| 作者 | Wei, R; Fang, ZT; Vasiliu, M; Dixon, DA; Andrews, L; Gong, Y |
| 刊名 | INORGANIC CHEMISTRY
 |
| 出版日期 | 2019 |
| 卷号 | 58期号:15页码:9796-9810 |
| 关键词 | DENSITY-FUNCTIONAL CALCULATIONS 2ND-ORDER PERTURBATION-THEORY COUPLED-CLUSTER THEORY MATRIX-ISOLATION OXYGEN DIFLUORIDE BENCHMARK CALCULATIONS ELECTRONIC-STRUCTURE VIBRATIONAL-SPECTRA TRIPLE EXCITATIONS CORRELATION-ENERGY |
| ISSN号 | 0020-1669 |
| DOI | 10.1021/acs.inorgchem.9b00822 |
| 文献子类 | 期刊论文 |
| 英文摘要 | A collection of 3d transition metal (V, Mn, Fe, Co, and Ni) oxyfluorides were prepared via the reactions of laser-ablated metal atoms and OF2 in an argon matrix, and the products were identified by infrared spectroscopy together with (OF2)-O-18 substitution. OMF(2 )is the major product from the reactions of metal atoms and OF2. The tetravalent metal center is coordinated to two fluorine atoms and one oxygen atom. Triatomic OMF molecules were observed in the reactions of V, Mn, Fe, and Co with OF2. In addition to OMF and OMF2 , OMnF3 and OFeF3 were also formed presumably via the reactions of OMnF and OFeF with F-2 resulting from photodecomposition of OF2. The seldom observed OF radical was produced in all of these experiments. Electronic structure calculations at the density functional theory and molecular orbital theory including electron correlation effects (CCSD(T) and CASPT2) levels are used to aid in the assignment of the structures. For OMF (M = Sc-Mn), the structures are bent and those for M = Fe-Cu are linear. The OMF2 molecules are optimized to be C-2 nu structures. Both OMF and OMF2 have a high spin ground state, with the exception of OCoF2 in which the ground state quartet is the lower energy structure. The M-O stretching frequency is a sensitive measure of the computational method in terms of the bond angle, the coupling of the M-O and M-F stretches, and the amount of spin on the oxygen. A bonding analysis in terms of the CAS orbitals shows that a number of the structures have a multireference character after M = Cr. Oxidation states of the metal are given based on the CASPT2 results. Heats of formation for the OMF and OMF2 are reported. |
| 语种 | 英语 |
| 源URL | [http://ir.sinap.ac.cn/handle/331007/32097]  |
| 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 |
| 作者单位 | 1.Chinese Acad Sci, Shanghai Inst Appl Phys, Dept Radiochem, Shanghai 201800, Peoples R China; 2.Univ Alabama, Dept Chem, Box 870336, Tuscaloosa, AL 35487 USA; 3.Univ Virginia, Dept Chem, Charlottesville, VA 22904 USA 4.Univ Chinese Acad Sci, Sch Nucl Sci & Technol, Beijing 100049, Peoples R China; |
| 推荐引用方式 GB/T 7714 | Wei, R,Fang, ZT,Vasiliu, M,et al. Infrared Spectroscopic and Theoretical Studies of the 3d Transition Metal Oxyfluoride Molecules[J]. INORGANIC CHEMISTRY,2019,58(15):9796-9810. |
| APA | Wei, R,Fang, ZT,Vasiliu, M,Dixon, DA,Andrews, L,&Gong, Y.(2019).Infrared Spectroscopic and Theoretical Studies of the 3d Transition Metal Oxyfluoride Molecules.INORGANIC CHEMISTRY,58(15),9796-9810. |
| MLA | Wei, R,et al."Infrared Spectroscopic and Theoretical Studies of the 3d Transition Metal Oxyfluoride Molecules".INORGANIC CHEMISTRY 58.15(2019):9796-9810. |
入库方式： OAI收割
来源：上海应用物理研究所
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