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The Energies of Atomic Orbitals03:21

The Energies of Atomic Orbitals

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In an atom, the negatively charged electrons are attracted to the positively charged nucleus. In a multielectron atom, electron-electron repulsions are also observed. The attractive and repulsive forces are dependent on the distance between the particles, as well as the sign and magnitude of the charges on the individual particles. When the charges on the particles are opposite, they attract each other. If both particles have the same charge, they repel each other.
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Atomic Orbitals02:44

Atomic Orbitals

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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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Electron Orbital Model01:18

Electron Orbital Model

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Orbitals are the areas outside of the atomic nucleus where electrons are most likely to reside. They are characterized by different energy levels, shapes, and three-dimensional orientations. The location of electrons is described most generally by a shell or principal energy level, then by a subshell within each shell, and finally, by individual orbitals found within the subshells.
The first shell is closest to the nucleus, and it has only one subshell with a single spherical orbital called the...
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Hybridization of Atomic Orbitals II03:35

Hybridization of Atomic Orbitals II

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sp3d and sp3d 2 Hybridization
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Hybridization of Atomic Orbitals I03:24

Hybridization of Atomic Orbitals I

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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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Fermi Level Dynamics01:12

Fermi Level Dynamics

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The vacuum level denotes the energy threshold required for an electron to escape from a material surface. It is usually positioned above the conduction band of a semiconductor and acts as a benchmark for comparing electron energies within various materials.
Electron affinity in semiconductors refers to the energy gap between the minimum of its conduction band and the vacuum level and it is a critical parameter in determining how easily a semiconductor can accept additional electrons.
The work...
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Excitonic Hamiltonians for Calculating Optical Absorption Spectra and Optoelectronic Properties of Molecular Aggregates and Solids
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高精度和强大的基于约束的轨道优化的核心激发.

Yannick Lemke1, Jörg Kussmann1, Christian Ochsenfeld1,2

  • 1Chair of Theoretical Chemistry, Department of Chemistry, Ludwig-Maximilians-Universität München, Butenandtstr. 5-13, Munich D-81377, Germany.

The journal of physical chemistry. A
|November 4, 2024
PubMed
概括

我们适应了基于约束的轨道优化激发状态方法 (COOX) 进行核心激发. 这种方法准确地预测了X射线吸收光谱,性能优于现有的方法.

科学领域:

  • 计算化学计算化学
  • 量子化学 是一个量子化学.
  • 频谱学是一种光谱学.

背景情况:

  • 核心激发,如K和L边缘,对于理解材料特性和化学过程至关重要.
  • 传统的方法,如线性响应时间依赖的DFT (LR-TDDFT),在准确计算核心激发能量方面面临挑战.
  • 基于约束的轨道优化激发状态方法 (COOX) 已经显示出对价值激发的承诺.

研究的目的:

  • 适应和验证COOX方法用于准确计算核心级电子激发.
  • 将COOX的适用性扩展到各种元素的K,L和M边缘激发.
  • 为了比较适应的COOX方法的性能与已建立的技术,如 ΔSCF 方法.

主要方法:

  • 开发一种COOX方法的旋转不受限制的变体,以处理核心激发.
  • 整合了三重净化方案和受约束的不受限制的哈特里-福克形式主义.
  • 包括标量相对论纠正和半经验旋转轨道合处理.

主要成果:

  • 适应的COOX方法在第二和第三周期原子的K和L边缘激发中实现了亚电子电压的准确性.
  • 该方法证明了对包括在内的较重元素的L和M边缘激发的计算可行性和数值稳定性.
  • COOX 显示了与 ΔSCF 方法相当或优于该方法的性能,并且具有更好的收性质.

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Last Updated: Jun 8, 2025

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结论:

  • 旋转不受限制的COOX方法是模拟核心激发的可靠和高效工具.
  • COOX提供了一个有前途的替代方案,可以准确和经济有效地预测X射线吸收光谱.
  • 这一进步有助于更深入地了解通过X射线光谱检测到的电子结构和化学动态.