Luo Zhen, Ma Yingjin, Liu Chungen, Ma Haibo
Key Laboratory of Mesoscopic Chemistry of MOE, School of Chemistry and Chemical Engineering, Nanjing University , Nanjing 210023, China.
Department of High Performance Computing Technology and Application Development, Computer Network Information Center, Chinese Academy of Sciences , Beijing 100190, China.
J Chem Theory Comput. 2017 Oct 10;13(10):4699-4710. doi: 10.1021/acs.jctc.7b00439. Epub 2017 Sep 27.
We improve the methodology to construct a complete active space-configuration interaction (CAS-CI) expansion for density-matrix renormalization group (DMRG) wave functions using a matrix-product state representation, inspired by the sampling-reconstructed CAS [SR-CAS; Boguslawski , K. ; J. Chem. Phys. 2011 , 134 , 224101 ] algorithm. In our scheme, the genetic algorithm, in which the "crossover" and "mutation" processes can be optimized based on quantum information theory, is employed when reconstructing a CAS-CI-type wave function in the Hilbert space. Analysis of results for ground and excited state wave functions of conjugated molecules, transition metal compounds, and a lanthanide complex illustrate that our scheme is very efficient for searching the most important CI expansions in large active spaces.
受采样重构完全活性空间（SR-CAS；博古斯拉夫斯基，K.；《化学物理杂志》，2011年，第134卷，第224101页）算法的启发，我们改进了使用矩阵乘积态表示为密度矩阵重整化群（DMRG）波函数构建完全活性空间-组态相互作用（CAS-CI）展开的方法。在我们的方案中，当在希尔伯特空间重构CAS-CI型波函数时，采用了遗传算法，其中“交叉”和“变异”过程可基于量子信息理论进行优化。对共轭分子、过渡金属化合物和镧系配合物的基态和激发态波函数的结果分析表明，我们的方案在搜索大活性空间中最重要的CI展开方面非常有效。
