Chair of Theoretical Chemistry and Center for Integrated Protein Science Munich (CIPSM), Department of Chemistry , University of Munich (LMU) , Butenandtstrasse 7 , 81377 Munich , Germany.
Max Planck Institute for Solid State Research, Heisenbergstrasse 1 , 70569 Stuttgart , Germany.
J Chem Theory Comput. 2018 Jun 12;14(6):3014-3024. doi: 10.1021/acs.jctc.8b00116. Epub 2018 May 15.
We introduce a new ansatz to compute hyperfine coupling constants of selected nuclei at the level of second-order Møller-Plesset perturbation (MP2) and double-hybrid density functional theory with reduced computational effort, opening the route to the analyis of hyperfine coupling constants of large molecular structures. Our approach is based on a reformulation of the canonical MP2 term in atomic orbitals, thus exploiting the locality of electron correlation. We show that a perturbation-including integral screening reduces the scaling behavior of the number of significant two-electron integrals to sublinear. This selected-nuclei approach allows for an efficient computation within scaled-opposite spin (SOS) RI-MP2 on massively parallelized architectures such as graphical processor units (GPUs), thus enabling studies on the influence of the environment on hyperfine coupling constants.
我们提出了一种新的方法，可在二阶 Møller-Plesset 微扰 (MP2) 和双杂交密度泛函理论的水平上，以较低的计算成本计算选定原子核的精细耦合常数，为分析大分子结构的精细耦合常数开辟了道路。我们的方法基于对原子轨道中规范 MP2 项的重新表述，从而利用了电子相关的局域性。我们表明，包含微扰的积分屏蔽将重要双电子积分数量的比例行为降低到次线性。这种选择核的方法允许在大规模并行化架构（如图形处理器单元 (GPU)）上进行缩放相反自旋 (SOS) RI-MP2 的高效计算，从而能够研究环境对精细耦合常数的影响。
