Lu Jun-Bo, Zhang Yang-Yang, Jiang Xue-Lian, Ye Lian-Wei, Li Jun
Fundamental Science Center of Rare Earths, Ganjiang Innovation Academy, Chinese Academy of Sciences, Ganzhou 341000, China.
Department of Chemistry and Guangdong Provincial Key Laboratory of Catalytic Chemistry, Southern University of Science and Technology, Shenzhen 518055, China.
J Chem Phys. 2024 Oct 7;161(13). doi: 10.1063/5.0228388.
The first-principles quantum chemical computations often scale as Nk (N = basis sets; k = 1-4 for linear scaling, Hartree-Fock or density functional theory methods), which makes the development of accurate pseudopotentials and efficient basis sets necessary ingredients in modeling of heavy elements such as lanthanides and actinides. Recently, we have developed 4f-in-core norm-conserving pseudopotentials and associated basis sets for the trivalent lanthanides [Lu et al., J. Chem. Theory Comput. 19, 82-96 (2023)]. In the present paper, we present a unified approach to optimize high-quality Gaussian basis sets for modeling and simulations of condensed-phase systems. The newly generated basis sets not only capture the low total energy and fairly reasonable condition number of overlap matrix of lanthanide-containing systems, but also exhibit good transferability and reproducibility. These advantages ensure the accuracy of the basis sets while avoiding linear dependency concern of atom-centered basis sets. The performance of the basis sets is further illustrated in lanthanide molecular and condensed-phase systems by using Gaussian-plane wave density functional approach of CP2K. These new basis sets can be of particular interest to model structurally complicated lanthanide molecules, clusters, solutions, and solid systems.
第一性原理量子化学计算通常按N^k进行缩放（N = 基组；对于线性缩放、哈特里-福克或密度泛函理论方法，k = 1 - 4），这使得开发精确的赝势和高效的基组成为镧系和锕系等重元素建模的必要组成部分。最近，我们为三价镧系元素开发了4f内芯守恒赝势和相关基组[Lu等人，《化学理论与计算杂志》19，82 - 96（2023）]。在本文中，我们提出了一种统一的方法来优化用于凝聚相系统建模和模拟的高质量高斯基组。新生成的基组不仅能捕捉含镧系元素系统的低总能和重叠矩阵相当合理的条件数，还具有良好的可转移性和可重复性。这些优点确保了基组的准确性，同时避免了以原子为中心的基组的线性相关性问题。通过使用CP2K的高斯平面波密度泛函方法，在镧系分子和凝聚相系统中进一步说明了这些基组的性能。这些新基组对于模拟结构复杂的镧系分子、团簇、溶液和固体系统可能特别有意义。
