Bischoff Florian A
Institut für Chemie, Humboldt-Universität zu Berlin, Unter den Linden 6, 10099 Berlin, Germany.
J Chem Phys. 2014 Nov 14;141(18):184106. doi: 10.1063/1.4901022.
In Paper I of this series [F. A. Bischoff, "Regularizing the molecular potential in electronic structure calculations. I. SCF methods," J. Chem. Phys. 141, 184105 (2014)] a regularized molecular Hamilton operator for electronic structure calculations was derived and its properties in SCF calculations were studied. The regularization was achieved using a correlation factor that models the electron-nuclear cusp. In the present study we extend the regularization to correlated methods, in particular the exact solution of the two-electron problem, as well as second-order many body perturbation theory. The nuclear and electronic correlation factors lead to computations with a smaller memory footprint because the singularities are removed from the working equations, which allows coarser grid resolution while maintaining the precision. Numerical examples are given.
在本系列的第一篇论文[F. A. 比肖夫，“电子结构计算中的分子势正则化。I. 自洽场方法”，《化学物理杂志》141, 184105 (2014)]中，推导了用于电子结构计算的正则化分子哈密顿算符，并研究了其在自洽场计算中的性质。正则化是通过一个模拟电子 - 核尖点的关联因子实现的。在本研究中，我们将正则化扩展到关联方法，特别是双电子问题的精确解以及二阶多体微扰理论。核和电子关联因子导致计算所需的内存占用更小，因为奇点从工作方程中被消除了，这使得在保持精度的同时可以采用更粗的网格分辨率。文中给出了数值示例。
