Exchange-hole dipole moment and the dispersion interaction revisited
Exchange-hole dipole moment and the dispersion interaction revisited
复制标题
DOI：
10.1063/1.2795701
复制
发表时间：
2007-10-21
影响因子：
4.4
通讯作者：
Johnson, Erin R.
中科院分区：
文献类型：
--
作者：
Becke, Axel D.;Johnson, Erin R.
最近，我们引入了一个基于交换空穴位置相关偶极矩的色散相互作用模型。太棒了。122、154104(2005年)]。最初的推导涉及简单的偶极感应偶极静电学，但有点启发式，缺乏严谨性。在这里，我们给出了闭包近似下基于二阶微扰理论的更令人满意的导数，并给出了相关相互作用积分的半经典求值。C-6、C-8和C-10色散系数的表达式以非常简单的方式得到。它们的值与H、He、Ne、Ar、Kr和Xe原子之间色散系数的从头算参考数据非常吻合。我们还强调了交换空穴对色散系数，特别是对C-6的贡献的重要性。(C)2007年美国物理研究所。[DOI：10.1063/1.2795701]
We have recently introduced a model of the dispersion interaction based on the position-dependent dipole moment of the exchange hole [J. Chem. Phys. 122, 154104 (2005)]. The original derivation, involving simple dipole-induced-dipole electrostatics, was somewhat heuristic, however, and lacking in rigor. Here we present a much more satisfying derivation founded on second-order perturbation theory in the closure approximation and a semiclassical evaluation of the relevant interaction integrals. Expressions for C-6, C-8, and C-10 dispersion coefficients are obtained in a remarkably straightforward manner. Their values agree very well with ab initio reference data on dispersion coefficients between the atoms H, He, Ne, Ar, Kr, and Xe. We also highlight the importance of the exchange-hole contribution to the dispersion coefficients, especially to C-6.(C) 2007 American Institute of Physics. [DOI: 10.1063/1.2795701]