和哈夫尼单基的电子结构
João G F Romeu1, Nickolas A Joyner1, Elliot Kaye1
1Department of Chemistry and Biochemistry, The University of Alabama, Shelby Hall, Tuscaloosa, Alabama 35487-0336, United States.
The journal of physical chemistry. A
|September 25, 2025
概括
高级量子计算准确地预测了ZrO,ZrS,HfO和HfS的潜在能量曲线和键解离能. 新的基准集提高了化合物的准确性,使理论结果与实验数据保持一致.
科学领域:
- 计算化学的计算化学
- 量子化学 是一个量子化学.
- 频谱学是一种光谱学.
背景情况:
- 对分子性质的准确理论预测对于理解化学键和反应性至关重要.
- 之前的研究可能在重金属化合物的基础选择或计算方法方面存在局限性.
- 实验数据为理论模型提供了基准.
研究的目的:
- 使用高层次量子化学方法计算ZrO,ZrS,HfO和HfS的最低电子状态的潜在能量曲线 (PEC).
- 开发和应用新的全电子基础套件用于 hafnium (Hf),以提高准确性,特别是当核心-价值分离较差时.
- 为了对光谱参数进行基准测试,并计算这些金属氧化物和硫化物的键解离能 (BDE).
主要方法:
- 高级ab initio合集群计算,特别是CCSD(T) 和旋转轨道内部合约的多引用配置与戴维森校正 (icMRCI+Q) 的相互作用.
- 开发和应用新的全电子基础集 (DK-4f) 对哈夫,改进有效核心潜力 (ECP).
- 对光谱参数的实验数据进行基准测试,并使用R3PI方法重新测量HfS的BDE.
主要成果:
- 成功预测了ZrO,ZrS,HfO和HfS最低状态的潜在能量曲线.
- 发现ZrO和ZrS的基本状态在icMRCI+Q水平上依赖于基数,但CCSD (T) 通过旋转轨道校正与实验一致.
- 计算的BDE与实验值非常一致,新测量的HfS BDE为576.8 ± 0.2 kJ/mol,阴离子BDE为494.4 ± 0.2 kJ/mol.
结论:
- 这项研究证明了高级量子化学方法的可靠性,特别是具有自旋轨道校正的CCSD,用于预测这些含金属分子的特性.
- 新开发的DK-4f基础集对于涉及化合物的准确计算至关重要,解决了ECP的局限性.
- 准确的BDE和最新的实验数据为了解Zr和Hf氧化物和硫化物的化学行为和稳定性提供了有价值的信息.
相关概念视频
02:42Ionic Crystal Structures
16.8K
Ionic crystals consist of two or more different kinds of ions that usually have different sizes. The packing of these ions into a crystal structure is more complex than the packing of metal atoms that are the same size.
Most monatomic ions behave as charged spheres, and their attraction for ions of opposite charge is the same in every direction. Consequently, stable structures for ionic compounds result (1) when ions of one charge are surrounded by as many ions as possible of the opposite...
Most monatomic ions behave as charged spheres, and their attraction for ions of opposite charge is the same in every direction. Consequently, stable structures for ionic compounds result (1) when ions of one charge are surrounded by as many ions as possible of the opposite...
16.8K
03:26Electron Configuration of Multielectron Atoms
64.5K
The alkali metal sodium (atomic number 11) has one more electron than the neon atom. This electron must go into the lowest-energy subshell available, the 3s orbital, giving a 1s22s22p63s1 configuration. The electrons occupying the outermost shell orbital(s) (highest value of n) are called valence electrons, and those occupying the inner shell orbitals are called core electrons. Since the core electron shells correspond to noble gas electron configurations, we can abbreviate electron...
64.5K
02:42Valence Bond Theory
11.2K
Coordination compounds and complexes exhibit different colors, geometries, and magnetic behavior, depending on the metal atom/ion and ligands from which they are composed. In an attempt to explain the bonding and structure of coordination complexes, Linus Pauling proposed the valence bond theory, or VBT, using the concepts of hybridization and the overlapping of the atomic orbitals. According to VBT, the central metal atom or ion (Lewis acid) hybridizes to provide empty orbitals of suitable...
11.2K
02:46Electron Configurations
25.4K
Electron configurations and orbital diagrams can be determined by applying the Aufbau principle (each added electron occupies the subshell of lowest energy available), Pauli exclusion principle (no two electrons can have the same set of four quantum numbers), and Hund’s rule of maximum multiplicity (whenever possible, electrons retain unpaired spins in degenerate orbitals).
The relative energies of the subshells determine the order in which atomic orbitals are filled (1s, 2s, 2p, 3s, 3p,...
The relative energies of the subshells determine the order in which atomic orbitals are filled (1s, 2s, 2p, 3s, 3p,...
25.4K
02:37Metallic Solids
20.5K
Metallic solids such as crystals of copper, aluminum, and iron are formed by metal atoms. The structure of metallic crystals is often described as a uniform distribution of atomic nuclei within a “sea” of delocalized electrons. The atoms within such a metallic solid are held together by a unique force known as metallic bonding that gives rise to many useful and varied bulk properties.
All metallic solids exhibit high thermal and electrical conductivity, metallic luster, and malleability....
All metallic solids exhibit high thermal and electrical conductivity, metallic luster, and malleability....
20.5K
02:46Crystal Field Theory - Tetrahedral and Square Planar Complexes
48.2K
Tetrahedral Complexes
Crystal field theory (CFT) is applicable to molecules in geometries other than octahedral. In octahedral complexes, the lobes of the dx2−y2 and dz2 orbitals point directly at the ligands. For tetrahedral complexes, the d orbitals remain in place, but with only four ligands located between the axes. None of the orbitals points directly at the tetrahedral ligands. However, the dx2−y2 and dz2 orbitals (along the Cartesian axes) overlap with the ligands less than the dxy,...
Crystal field theory (CFT) is applicable to molecules in geometries other than octahedral. In octahedral complexes, the lobes of the dx2−y2 and dz2 orbitals point directly at the ligands. For tetrahedral complexes, the d orbitals remain in place, but with only four ligands located between the axes. None of the orbitals points directly at the tetrahedral ligands. However, the dx2−y2 and dz2 orbitals (along the Cartesian axes) overlap with the ligands less than the dxy,...
48.2K