时间依赖的多配置的短距离密度函数理论与一般化的价值键波函数
Michał Hapka1, Hans Jørgen Aa Jensen2
1Faculty of Chemistry, University of Warsaw, ul. L. Pasteura 1, 02-093 Warsaw, Poland.
The journal of physical chemistry. A
|September 29, 2025
概括
我们介绍了依赖时间的通用价值键范围分离密度函数理论 (TD-GVB-srDFT),用于精确计算分子性质. 这种方法增强了激发能量和旋转-旋转合常量,为现有的计算模型提供了强大的替代方案.
科学领域:
- 计算化学计算化学
- 量子化学 是一个量子化学.
- 理论化学 理论化学
背景情况:
- 精确计算分子性质在化学中至关重要.
- 像GVB-PP这样的现有方法在捕获动态相关性方面存在局限性.
- 范围分离密度函数理论提供了一种包含动态相关性的方法.
研究的目的:
- 介绍TD-GVB-srDFT的理论和实施.
- 为了对TD-GVB-srDFT进行激发能和旋转合常数的基准测试.
- 将TD-GVB-srDFT与其他理论方法进行比较.
主要方法:
- 时间依赖的多配置范围分离密度函数理论 (TD-GVB-srDFT).
- 一般化的价值键完美配对 (GVB-PP) 波函数.
- 波函数优化和线性响应的直接赫西安技术.
- 库伦电位的范围分离.
- 对于三重激发的通用塔姆-丹科夫近似 (gTDA).
主要成果:
- 与GVB-PP相比,TD-GVB-srDFT显著提高了激发能量.
- 激发能量的精度与CAS-srDFT (平均绝对偏差为0.2 eV) 相似.
- GVB-srDFT准确地计算了有机分子的自旋-自旋合常量.
- 无论是GVB-srDFT还是CAS-srDFT都准确地复制了具有gTDA的过渡金属复合体中的金属合.
结论:
- TD-GVB-srDFT为电子结构计算提供了一种计算效率高,准确的方法.
- 该方法在基础的GVB-PP模型中提供了显著的改进.
- TD-GVB-srDFT是研究分子特性的一个有前途的工具,特别是在具有显著动态相关性的情况下.
更多相关视频
12:11Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry
Published on: April 8, 2020
8.7K
08:54Vibrational Spectra of a N719-Chromophore/Titania Interface from Empirical-Potential Molecular-Dynamics Simulation, Solvated by a Room Temperature Ionic Liquid
Published on: January 25, 2020
6.0K
相关概念视频
02:38Valence Bond Theory and Hybridized Orbitals
27.8K
According to valence bond theory, a covalent bond results when: (1) an orbital on one atom overlaps an orbital on a second atom, and (2) the single electrons in each orbital combine to form an electron pair. The strength of a covalent bond depends on the extent of overlap of the orbitals involved. Maximum overlap is possible when the orbitals overlap on a direct line between the two nuclei.
A σ bond (single bond in a Lewis structure) is a covalent bond in which the electron density is...
A σ bond (single bond in a Lewis structure) is a covalent bond in which the electron density is...
27.8K
02:40MO Theory and Covalent Bonding
13.5K
The molecular orbital theory describes the distribution of electrons in molecules in a manner similar to the distribution of electrons in atomic orbitals. The region of space in which a valence electron in a molecule is likely to be found is called a molecular orbital. Mathematically, the linear combination of atomic orbitals (LCAO) generates molecular orbitals. Combinations of in-phase atomic orbital wave functions result in regions with a high probability of electron density, while...
13.5K
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
02:45Valence Bond Theory
49.7K
Overview of Valence Bond Theory
49.7K
03:51Molecular Orbital Theory II
26.9K
Molecular Orbital Energy Diagrams
26.9K
02:35Molecular Orbital Theory I
46.9K
Overview of Molecular Orbital Theory
46.9K