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The Aufbau Principle and Hund's Rule03:02

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To determine the electron configuration for any particular atom, we can build the structures in the order of atomic numbers. Beginning with hydrogen, and continuing across the periods of the periodic table, we add one proton at a time to the nucleus and one electron to the proper subshell until we have described the electron configurations of all the elements. This procedure is called the aufbau principle, from the German word aufbau (“to build up”). Each added electron occupies the...
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The mathematical expression known as the wave function, ψ, contains information about each orbital and the wavelike properties of electrons in an isolated atom. When atoms are bound together in a molecule, the wave functions combine to produce new mathematical descriptions that have different shapes. This process of combining the wave functions for atomic orbitals is called hybridization and is mathematically accomplished by the linear combination of atomic orbitals. The new orbitals that...
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An atomic orbital represents the three-dimensional regions in an atom where an electron has the highest probability to reside. The radial distribution function indicates the total probability of finding an electron within the thin shell at a distance r from the nucleus. The atomic orbitals have distinct shapes which are determined by l, the angular momentum quantum number. The orbitals are often drawn with a boundary surface, enclosing densest regions of the cloud. 
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Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry
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通过扰乱性分析改善压制合集群的构建.

Harrison Tuckman1, Ziheng Ma1, Eric Neuscamman1,2

  • 1Department of Chemistry, University of California, Berkeley, California 94720, United States.

Journal of chemical theory and computation
|April 10, 2025
PubMed
概括

我们增强了Aufbau抑制合集群理论,以准确计算激发状态. 这种方法提高了各种激发的精度,同时保持了计算效率,超过了电荷转移状态的现有方法.

科学领域:

  • 量子化学 是一个量子化学.
  • 计算光谱学是一种计算光谱学.
  • 电子兴奋状态 电子兴奋状态

背景情况:

  • 精确计算电子激发状态对于理解光物理和光化学过程至关重要.
  • 现有的方法,如运动方程合集群理论,在某些激发类型的准确性和计算成本方面面临挑战.
  • Aufbau抑制合集群 (ASCC) 理论提供了一个有前途的框架,但需要对激发状态进行进一步的细化.

研究的目的:

  • 为了提高Aufbau抑制合集群理论的准确性,用于各种类型的电子激发.
  • 与基态合集群方法相比,保持领先阶段项的计算效率.
  • 为了实现电荷转移激发的高精度,超越了既定的方法.

主要方法:

  • 扰动性分析以指导ASCC理论的改进.
  • 开发一个自旋适应和更高效的ASCC的实施.
  • 系统地识别和对振幅进行优先排序,用于激发状态计算.
  • 理论的部分线性化,以减轻 Aufbau 抑制的副作用.

主要成果:

  • 对于简单的单次激发,多配置的单次激发和电荷转移激发,实现了高精度.
  • 保持了领先顺序项的计算成本,与地面状态合集群可比.

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  • 证明了电荷转移状态的平均无符号误差,比运动方程合集群理论低0.25 eV.
  • 确定了激发状态和基本状态ASCC理论之间的振幅优先级的关键差异.
  • 结论:

    • 增强的ASCC理论提供了一个计算效率高和高度准确的方法来计算电子激发状态.
    • 与现有的最先进的方法相比,开发的方法在电荷转移激发方面提供了显著的改进.
    • 这些发现强调了振幅优先和部分线性化在ASCC理论中对于准确的激发状态计算的重要性.