Okoshi Masaki, Nakai Hiromi
Department of Chemistry and Biochemistry, School of Advanced Science and Engineering, Waseda University, Tokyo, 169-8555, Japan.
J Comput Chem. 2014 Jul 30;35(20):1473-80. doi: 10.1002/jcc.23617. Epub 2014 Apr 24.
The Lagrange interpolation of molecular orbital (LIMO) method, which reduces the number of self-consistent field iterations in ab initio molecular dynamics simulations with the Hartree-Fock method and the Kohn-Sham density functional theories, is extended to the theory of multiconfigurational wave functions. We examine two types of treatments for the active orbitals that are partially occupied. The first treatment, as denoted by LIMO(C), is a simple application of the conventional LIMO method to the union of the inactive core and the active orbitals. The second, as denoted by LIMO(S), separately treats the inactive core and the active orbitals. Numerical tests to compare the two treatments clarify that LIMO(S) is superior to LIMO(C). Further applications of LIMO(S) to various systems demonstrate its effectiveness and robustness.
分子轨道的拉格朗日插值（LIMO）方法，可减少使用哈特里 - 福克方法和科恩 - 沙姆密度泛函理论的从头算分子动力学模拟中的自洽场迭代次数，该方法已扩展到多组态波函数理论。我们研究了对部分占据的活性轨道的两种处理方式。第一种处理方式，记为LIMO(C)，是将传统的LIMO方法简单应用于非活性核心和活性轨道的并集。第二种，记为LIMO(S)，分别处理非活性核心和活性轨道。比较这两种处理方式的数值测试表明，LIMO(S)优于LIMO(C)。LIMO(S)在各种系统中的进一步应用证明了其有效性和稳健性。
