空穴-粒子对称的图形酉群方法在多参考态组态相互作用中的应用  

Graphical unitary group approach based on hole-particle symmetry using in multi-reference configuration interaction

作　　者：索兵兵[1] 雷依波[2,3] 王育彬[1] 文振翼[1] 

机构地区：[1]西北大学现代物理研究所,西安710069 [2]合成与天然功能分子化学教育部重点实验室 [3]西北大学化学与材料科学学院,西安710069

出　　处：《中国科学：化学》2015年第12期1325-1336,共12页SCIENTIA SINICA Chimica

基　　金：国家自然科学基金(21173166,21473134,21203147);陕西省自然科学基础研究计划(2014JQ2060)资助

摘　　要：空穴-粒子对称的图形酉群方法(graphic unitary group approach,GUGA)被用于发展高效的多参考态组态相互作用(multi-reference configuration interaction,MRCI)程序.通过将轨道空间划分为双占据轨道、活性轨道和外轨道空间分别处理,耦合系数可以写为三个空间片段因子的乘积.由于仅需搜索和保存活性空间的片段因子,其余两个空间的片段因子可以根据图形类型直接确定,从而避免了部分耦合系数随内空间增大无法保存的难题,使MRCI可被用于超过32个内轨道的计算.空穴一粒子对称允许我们将MRCI的组态空间按照双占据空间空穴数和外空间电子数自然划分为子组态空间,内收缩函数可以分别定义在子组态空间中.在此基础上,我们提出了基于GUGA的内收缩MRCI新方案并程序化.测试表明,未收缩组态空间超过10亿的MRCI已成为可以在普通工作站上完成的常规计算.Graphical unitary group approach（GUGA） based on the hole-particle symmetry is used to develop an efficient multi-reference configuration interaction（MRCI） algorithm.By dividing the orbital into the doubly occupied,active and external orbitals,the coupling coefficient can be calculated as the product of three segmental factors in each orbital space.Only segmental factors in the active space needs to be stored that reduces the storage requirements significantly.Therefore,MRCI calculation with more than 32 internal orbitals can be performed by our program easily.The application of hole-particle symmetry also allows us to divide the configuration space into a serial of sub-CI spaces according to the number of holes in the doubly occupied space and the number of electrons in the external space.The internal contraction of configuration space can be performed within the individual sub-CI space.Consequently,a new internally contracted MRCI（ic-MRCI） algorithm based on GUGA is proposed and developed.Benchmark calculations illustrate that the large scale MRCI calculation with several billions of un-contracted configuration state functions（CSFs） has already become a routine task.

关 键 词：多参考态组态相互作用 图形酉群方法 空穴-粒子对称 内收缩组态 

分 类 号：O64[理学—物理化学]