精确交换和实证分散在密度函数理论为基础的三体非共价相互作用中的作用
1Department of Chemistry, University of Reading, Whiteknights Campus, Reading RG6 6UR, U.K.
The journal of physical chemistry. A
|September 25, 2024
概括
密度函数理论 (DFT) 方法准确计算三体相互作用能量. 包括Hartree-Fock交换或分散校正可以提高准确性,建议使用CAM-B3LYP-D3BJ,B97D3和oB97XD函数.
科学领域:
- 计算化学的计算化学
- 量子化学 是一个量子化学.
- 理论化学 理论化学
背景情况:
- 精确计算相互作用能量在化学中至关重要.
- 三体相互作用在分子系统中起着重要作用.
- 密度函数理论 (DFT) 是用于电子结构计算的广泛使用的方法.
研究的目的:
- 评估各种DFT方法的性能,用于计算总和三体相互作用能量.
- 为了将DFT结果与高级合集群理论 (CCSD) /CBS基准进行比较.
- 为了确定准确可靠的DFT函数,用于三体相互作用计算.
主要方法:
- 计算是在一个基准三体系统的基准组上进行的.
- 采用了一系列DFT方法,包括使用Hartree-Fock交换和实证分散校正的方法.
- 使用增强相关性一致的基准集评估了基准集的收率,高达四倍-ζ.
- 结果与已建立的CCSD (T) /CBS数据进行了比较.
主要成果:
- 包括Hartree-Fock交换和经验分散校正显著提高了三体相互作用的DFT方法的准确性.
- 发现 aug-cc-pVTZ 基数为这些计算而足够接近.
- 对于全球和地方的最低结构,DFT方法的准确性相似.
- 在CAM-B3LYP-D3BJ,B97D3和 ωB97XD函数中显示出高精度.
结论:
- DFT方法,特别是那些包含Hartree-Fock交换或分散校正的方法,对于计算三体相互作用能量是可靠的.
- 推的函数 (CAM-B3LYP-D3BJ,B97D3, ωB97XD) 提供了与高级理论相比的准确结果.
- 这些发现为在涉及三体相互作用的计算化学研究中选择适当的DFT方法提供了指导.
相关概念视频
01:24Van der Waals Interactions
63.6K
Atoms and molecules interact with each other through intermolecular forces. These electrostatic forces arise from attractive or repulsive interactions between particles with permanent, partial, or temporary charges. The intermolecular forces between neutral atoms and molecules are ion–dipole, dipole–dipole, and dispersion forces, collectively known as van der Waals forces.
63.6K
03:13Intermolecular Forces
57.9K
Atoms and molecules interact through bonds (or forces): intramolecular and intermolecular. The forces are electrostatic as they arise from interactions (attractive or repulsive) between charged species (permanent, partial, or temporary charges) and exist with varying strengths between ions, polar, nonpolar, and neutral molecules. The different types of intermolecular forces are ion–dipole, dipole–dipole, hydrogen bonds, and dispersion; among these, dipole–dipole, hydrogen...
57.9K
03:06The Pauli Exclusion Principle
35.5K
The arrangement of electrons in the orbitals of an atom is called its electron configuration. We describe an electron configuration with a symbol that contains three pieces of information:
35.5K
04:01Real Gases: Effects of Intermolecular Forces and Molecular Volume Deriving Van der Waals Equation
34.5K
Thus far, the ideal gas law, PV = nRT, has been applied to a variety of different types of problems, ranging from reaction stoichiometry and empirical and molecular formula problems to determining the density and molar mass of a gas. However, the behavior of a gas is often non-ideal, meaning that the observed relationships between its pressure, volume, and temperature are not accurately described by the gas laws.
34.5K
02:40MO Theory and Covalent Bonding
10.3K
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...
10.3K
02:46Crystal Field Theory - Tetrahedral and Square Planar Complexes
41.7K
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,...
41.7K