氢分子间色散相互作用能的自然轨道泛函

理论上对分子间色散相互作用能的精确计算一直是个难点问题.密度矩阵泛函基于非定域量一阶密度矩阵为基本变量,它与色散相互作用起源于电子间的非定域关联特性相吻合.论文以最简单的氢分子为研究对象,通过分析两相互平行的氢分子间色散相互作用能,构造出了该体系中色散相互作用能的自然轨道泛函.结果表明:描述该体系中色散相互作用能的自然轨道泛函形式为包含有4个轨道的非交换和库伦积分.该结果对发展色散相互作用能的密度矩阵泛函理论具有重要的参考价值.

Modelling the dispersion interaction between hydrogen molecules with natural orbital functional

It is still an unsolved problem in theory to calculate the dispersion interaction accurately. Density matrix functional theory takes non-local one-order density matrix as the fundamental variable, which is in well consistent with the physical nature of dispersion interaction.. In the present paper, the dispersion interaction between two hydrogen molecules has been well studied. The natural orbital functional is formulated to describe the dispersion interaction of this system. It is shown that the natural orbital functional of dispersion interaction between two hydrogen molecules is not the usually used exchange or coulomb integrals.