Giovannini Tommaso, Koch Henrik
Department of Chemistry, Norwegian University of Science and Technology, 7491 Trondheim, Norway.
Scuola Normale Superiore, Piazza dei Cavalieri 7, 56126 Pisa, Italy.
J Chem Theory Comput. 2021 Jan 12;17(1):139-150. doi: 10.1021/acs.jctc.0c00737. Epub 2020 Dec 18.
We present a novel energy-based localization procedure able to localize molecular orbitals into predefined spatial regions. The method is defined in a multiscale framework based on the multilevel Hartree-Fock approach. In particular, the system is partitioned into active and inactive fragments. The localized molecular orbitals are obtained maximizing the repulsion between the two fragments. The method is applied to several cases including both conjugated and non-conjugated systems. Our multiscale approach is compared with reference values for both ground-state properties, such as dipole moments, and local excitation energies. The proposed approach is useful to extend the application range of high-level electron correlation methods. In fact, the reduced number of molecular orbitals can lead to a large reduction in the computational cost of correlated calculations.
我们提出了一种基于能量的新型定位程序，该程序能够将分子轨道定位到预定义的空间区域。该方法是在基于多级Hartree-Fock方法的多尺度框架中定义的。具体而言，系统被划分为活性片段和非活性片段。通过最大化两个片段之间的排斥力来获得定域分子轨道。该方法应用于包括共轭和非共轭体系在内的多种情况。我们的多尺度方法与基态性质（如偶极矩）和局部激发能的参考值进行了比较。所提出的方法有助于扩展高水平电子相关方法的应用范围。事实上，减少分子轨道的数量可以大幅降低相关计算的计算成本。
