基于空穴-粒子对偶的内收缩多参考态二级微扰理论

Internally contracted multi-reference second order perturbation theory based on hole-particle symmetry

本文介绍了一种新的基于图形酉群方法和空穴-粒子对偶的内收缩多参考态二级微扰理论方法.此方法可以简便地实现任意组态空间的内收缩,从而大大降低微扰矩阵元的计算量.初步测试结果表明,我们的方法完全避免了侵入态问题,也解决了态兼并问题,而二茂铁自旋态分裂能和二氧化铜氨络合物两种同分异构体相对稳定性的计算证实,我们的方法在中等分子体系计算中精度较高.

We present an internally contracted multi-reference second order perturbation theory employing the graphical unitary group approach（GUGA） and hole-particle symmetry.It is very convenient to realize internal contraction of any configuration space,reducing the performance of computing perturbation matrix elements.The preliminary tests show that our method completely avoids intruder state and deals with state degenerate problem.The spin-state splittings of ferrocene and energy difference between two isomers of di-copper complexes of prove that it is relatively accurate for our method to calculate medium molecular systems.