重元素体系的电子动量谱学研究
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摘要
经过近四十年的发展,电子动量谱学以其同时测量物质中电子的能量分布和动量分布的独特优势,已经成为研究物质的电子结构、电子关联效应和电离机制的强有力工具。其应用价值已经在物理、化学、生物等多个学科的发展和应用中得到了充分体现。目前,随着第三代动量谱仪分辨率和探测效率的不断提高,电子动量谱学可以深入到一些新的研究领域。此外,相对论量子化学计算近年来发展迅速,结合相对论量子化学,我们可以开展重元素体系的电子动量谱学研究。
论文工作的主要目标是将相对论量子化学计算与电子动量谱学实验结合起来,对重元素体系的外价轨道电子分布的相关问题展开研究。相对论量子化学计算与电子动量谱学的结合是一个全新的课题,没有前人经验可以借鉴,难度较大。论文工作首先熟练掌握了支持相对论量子化学计算的ADF软件的使用方法,在此基础上编写相关程序,成功实现从ADF软件的输出文件中导出理论动量谱。这也为电子动量谱学开辟了研究重元素体系的全新前沿领域,对于实验室的发展有重要的意义。
论文首先从研究简单的氙和氪两种重元素原子入手,结合最新的电子动量谱实验数据,研究了氙、氪外价p轨道的相对论效应。然后研究深入到含重元素的双原子分子I_2和Au_2,通过比较它们外价轨道非相对论和相对论量子化学计算下动量分布的差异,揭示相对论效应对于其外价轨道电子分布的影响。最终,把我们的研究对象扩展到含重元素多原子分子上。
我们对六羰基钨和二茂铁两种分子的外价轨道进行了电子动量谱的实验测量,结合非相对论和相对论量子化学计算,对其外价轨道中的相对论效应,扭曲波效应和振动效应进行了系统的分析。此外,我们还对CF_3I分子的5e_(3/2)和5e_(1/2)轨道的相对论效应给出了最新的理论解释,对UF_6分子的外价轨道电子分布中相对论效应的影响作出了理论预测。
Electron momentum spectroscopy (EMS), with a history near 40 years, has been a powerful tool for investigating of electronic structure, electronic correlation effects and ionization mechanism in matters. EMS can directly measure the electron energy and momentum density distributions of matter, and its application has been extend to the fields of physics, chemistry, and biology. With the improvement of energy and momentum resolutions, electron momentum spectrometer can study some new and valuable areas, which were very difficult in past. In addition, the rapidly developed relativistic quantum chemistry theory has made possible the EMS study of heavy elements systems.
The main goal of this thesis is to combine the relativistic quantum chemistry calculation with EMS experiments to study valence electronic structures of heavy elements system. The combination of relativistic quantum chemistry and EMS is a new research area. There was no experience can be used for reference, therefore this area is full of difficulties and challenges.
After learning how to use the relativistic quantum chemistry program ADF, an interface program was successfully complied to generate theoretical momentum distributions from the standard ADF output file, which made EMS study extend to the systems containing heavy elements. This program will be very helpful for our laboratory future development.
The relativistic effects in the outer valence p orbital of Xenon and Krypton were investigated using high resolution EMS experiments incooperating with relativistic chemisty calculations. The comparions of non-relativistic and relativistic theoretical momentum profile revealed that the relativistic effects have remarkable influences on the electron density distributions of diatomic molecules I_2 and Au_2.
The outer valence orbitals of tungsten hexacarbonyl and ferrocene were measured using our third-generation electron momentum spectrometer. Incooperation with non-relativistic and relativistic calculations, the relativistic, distorted-wave and vibrational effects in the outer valence orbitals of these two polyatomic molecules were investigated systematically. Moreover, the experimental electron momentum spectra of 5e_(1/2) and 5e_(3/2) orbitals of CF_3I were interpreted with relativistic calculations, and relativistic effects in the valence orbital of UF_6 were predicted in theory.
论文工作的主要目标是将相对论量子化学计算与电子动量谱学实验结合起来,对重元素体系的外价轨道电子分布的相关问题展开研究。相对论量子化学计算与电子动量谱学的结合是一个全新的课题,没有前人经验可以借鉴,难度较大。论文工作首先熟练掌握了支持相对论量子化学计算的ADF软件的使用方法,在此基础上编写相关程序,成功实现从ADF软件的输出文件中导出理论动量谱。这也为电子动量谱学开辟了研究重元素体系的全新前沿领域,对于实验室的发展有重要的意义。
论文首先从研究简单的氙和氪两种重元素原子入手,结合最新的电子动量谱实验数据,研究了氙、氪外价p轨道的相对论效应。然后研究深入到含重元素的双原子分子I_2和Au_2,通过比较它们外价轨道非相对论和相对论量子化学计算下动量分布的差异,揭示相对论效应对于其外价轨道电子分布的影响。最终,把我们的研究对象扩展到含重元素多原子分子上。
我们对六羰基钨和二茂铁两种分子的外价轨道进行了电子动量谱的实验测量,结合非相对论和相对论量子化学计算,对其外价轨道中的相对论效应,扭曲波效应和振动效应进行了系统的分析。此外,我们还对CF_3I分子的5e_(3/2)和5e_(1/2)轨道的相对论效应给出了最新的理论解释,对UF_6分子的外价轨道电子分布中相对论效应的影响作出了理论预测。
Electron momentum spectroscopy (EMS), with a history near 40 years, has been a powerful tool for investigating of electronic structure, electronic correlation effects and ionization mechanism in matters. EMS can directly measure the electron energy and momentum density distributions of matter, and its application has been extend to the fields of physics, chemistry, and biology. With the improvement of energy and momentum resolutions, electron momentum spectrometer can study some new and valuable areas, which were very difficult in past. In addition, the rapidly developed relativistic quantum chemistry theory has made possible the EMS study of heavy elements systems.
The main goal of this thesis is to combine the relativistic quantum chemistry calculation with EMS experiments to study valence electronic structures of heavy elements system. The combination of relativistic quantum chemistry and EMS is a new research area. There was no experience can be used for reference, therefore this area is full of difficulties and challenges.
After learning how to use the relativistic quantum chemistry program ADF, an interface program was successfully complied to generate theoretical momentum distributions from the standard ADF output file, which made EMS study extend to the systems containing heavy elements. This program will be very helpful for our laboratory future development.
The relativistic effects in the outer valence p orbital of Xenon and Krypton were investigated using high resolution EMS experiments incooperating with relativistic chemisty calculations. The comparions of non-relativistic and relativistic theoretical momentum profile revealed that the relativistic effects have remarkable influences on the electron density distributions of diatomic molecules I_2 and Au_2.
The outer valence orbitals of tungsten hexacarbonyl and ferrocene were measured using our third-generation electron momentum spectrometer. Incooperation with non-relativistic and relativistic calculations, the relativistic, distorted-wave and vibrational effects in the outer valence orbitals of these two polyatomic molecules were investigated systematically. Moreover, the experimental electron momentum spectra of 5e_(1/2) and 5e_(3/2) orbitals of CF_3I were interpreted with relativistic calculations, and relativistic effects in the valence orbital of UF_6 were predicted in theory.
引文
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[3] McCarthy I E, Weigold E. Electron momentum spectroscopy of atoms and molecules. Rep. Prog. Phys., 1991, 54: 789-879.
[4] Coplan M A, Moore J H, Doering J P. (e,2e) spectroscopy. Rev. Mod. Phys., 1994, 66(3): 985-1014.
[5]陈学俊,郑延友.电子动量谱学的原理和应用.北京:清华大学出版社, 2000.
[6]郁伟忠.正电子物理及其应用.北京:科学出版社, 2003:124-134.
[7] Fukui K. Orbital Pattern Rationale in Chemical Empiricism. International J. Quantum Chem., 1977, 12: 277-288.
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